JP5400341B2 - Scale-like iron oxide particles having magnetite structure and use thereof - Google Patents
Scale-like iron oxide particles having magnetite structure and use thereof Download PDFInfo
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Description
本発明は、化粧料、塗料、合成樹脂、インキ、合成皮革および壁紙等、幅広い分野で有用な光輝性を有し黒色を呈する鱗片状酸化鉄粒子ならびにその使用に関するものである。 TECHNICAL FIELD The present invention relates to scaly iron oxide particles exhibiting blackness and brightness that are useful in a wide range of fields such as cosmetics, paints, synthetic resins, inks, synthetic leather and wallpaper, and uses thereof.
光輝性を有し黒色を呈する光沢顔料としては、天然の鱗片状酸化鉄粒子および合成鱗片状酸化鉄粒子において、その色調が黒色に近いものがあるが、いずれもヘマタイト構造であるために赤みがかったものであり、加えて天然の鱗片状酸化鉄粒子は粒子形状が不均一であり光輝性においても劣るため、もっぱら建築物の防錆塗料用途に使用されている。 Glossy pigments that have a brilliant black color are natural flaky iron oxide particles and synthetic flaky iron oxide particles that have a color tone close to black, but both are reddish because of their hematite structure. In addition, natural scaly iron oxide particles are non-uniform in particle shape and inferior in luster, and are therefore used exclusively for building anticorrosive coatings.
特許文献１は、酸化アルミニウムを固溶体中に含有する酸化鉄基材の小片型状顔料であり、表面に亜鉛、ジルコン、チタン、クロム、ケイ素、スズおよびビスマスの各酸化物を付着させ、還元およびアニーリングする黒色顔料を開示している。しかし該顔料は、小片型状顔料と称しているものの具体的な粒径が不明である。さらには鱗片状酸化鉄粒子表面の二酸化チタン水和物層または二酸化チタン層の厚さを制御することによりその色調を種々変化させることはできるものの、当該被覆層の結晶性は小さく、表面平滑性にも劣るため散乱反射光を生じやすく、光沢顔料として重要な特性である光輝性は基体顔料の鱗片状酸化鉄粒子のそれと比較すると弱いとの欠点を有している。 Patent Document 1 is a small pigment of an iron oxide base material containing aluminum oxide in a solid solution. Each oxide of zinc, zircon, titanium, chromium, silicon, tin and bismuth is attached to the surface, and reduced and reduced. A black pigment for annealing is disclosed. However, although the pigment is called a small piece pigment, the specific particle size is unknown. Furthermore, although the color tone can be changed variously by controlling the thickness of the titanium dioxide hydrate layer or titanium dioxide layer on the surface of the scaly iron oxide particles, the crystallinity of the coating layer is small, and the surface smoothness Therefore, it is easy to generate scattered reflected light, and the glittering property which is an important characteristic as a glossy pigment has a defect that it is weaker than that of the scaly iron oxide particles of the base pigment.
特許文献２では、常圧下における反応であり、オートクレーブ等の特殊な装置を必要としないので、工業的、経済的に有利であると説明している。しかしながら、この方法で得られる板状ハイドロタルサイト型微粒子粉末は板面径が０．５μｍ未満であるために、光輝性に劣るとの欠点を有している。 In Patent Document 2, it is a reaction under normal pressure, and a special apparatus such as an autoclave is not required, so that it is industrially and economically advantageous. However, the plate-like hydrotalcite-type fine particle powder obtained by this method has a disadvantage that the plate surface diameter is less than 0.5 μm, and therefore, the glitter is inferior.
酸化鉄系の光沢顔料では鱗片状あるいは板状の雲母、ガラスフレーク、アルミナ等に種々の金属酸化物を被覆したものが知られている。しかしながらこれらは金属酸化物被覆層が単一結晶ではないために、散乱反射光を生じやすく先鋭な光輝性を得にくい。さらには種々の塗料や樹脂等に配合加工する過程で金属酸化物被覆層が基体から剥離し、色調が変化するとの欠点を有する。 Iron oxide-based luster pigments are known in which various metal oxides are coated on scale-like or plate-like mica, glass flakes, alumina and the like. However, since the metal oxide coating layer is not a single crystal, it is easy to generate scattered reflected light, and it is difficult to obtain sharp glitter. Furthermore, there is a drawback that the metal oxide coating layer peels off from the substrate in the process of blending with various paints and resins, and the color tone changes.
この種の黒色の光輝性顔料として、特許文献３では、薄板状粉体表面に低次酸化チタンの被覆を行い、還元と酸化を行い黒色真珠光沢粉体を開示している。しかしながら低結晶性の低次酸化チタンは本質的に不安定であり、二酸化チタンに変化してその色調が変化するという欠点を有している。加えて該顔料の製造には真空状態８００℃という反応装置を必要とすること、高価な金属チタンを分級で取り除く必要があり収率の問題、還元と酸化の２段の長い製造工程を必要とするなどの問題も抱えている。 As this type of black bright pigment, Patent Document 3 discloses a black pearly luster powder that is coated with low-order titanium oxide on the surface of a thin plate-like powder, reduced and oxidized. However, low-crystalline low-order titanium oxide is inherently unstable, and has the disadvantage of changing its color tone to titanium dioxide. In addition, the production of the pigment requires a reaction apparatus having a vacuum state of 800 ° C., expensive metal titanium must be removed by classification, yield problems, and a long and two-stage production process of reduction and oxidation is required. I also have problems such as.
このように従来技術による光輝性を有する黒色光沢顔料は、十分な光輝性を有しているとは言い難いものであった。 Thus, it is difficult to say that the black glossy pigment having the glitter according to the prior art has sufficient glitter.
従って、本発明の目的は、従来の板状あるいは鱗片状の酸化鉄顔料の欠点を有さない黒色光沢顔料およびその用途を提供することにある。 Accordingly, an object of the present invention is to provide a black luster pigment that does not have the disadvantages of conventional plate-like or scale-like iron oxide pigments and uses thereof.
本発明者らは、前記の黒色光沢顔料が有する欠点を持たない新しい黒色光沢顔料を開発する為鋭意研究を重ねた結果、ヘマタイト構造を有するＡｌ含有鱗片状酸化鉄粒子を還元し、所定の寸法としたマグネタイト構造を有する鱗片状酸化鉄粒子が、従来技術による欠点を有さない黒色光沢顔料であるとの知見を得、この知見に基づいて本発明を完成させるに至った。なお、本発明でいう「鱗片状」とは概ね六角形、あるいは、その辺が崩れた薄片形状の粒子形状をいい、代表的には後述する図１の走査型電子顕微鏡写真に示される粒子形態をいう。 As a result of intensive research to develop a new black luster pigment that does not have the disadvantages of the black luster pigment, the present inventors have reduced Al-containing flaky iron oxide particles having a hematite structure and have a predetermined size. The inventors have obtained knowledge that the flaky iron oxide particles having a magnetite structure as described above are black glossy pigments that do not have the disadvantages of the prior art, and have completed the present invention based on this knowledge. The “scale-like” as used in the present invention means a hexagonal shape or a thin piece-like particle shape whose sides are broken, and is typically a particle form shown in a scanning electron micrograph of FIG. Say.
すなわち、本発明の鱗片状酸化鉄粒子は、鱗片形状を有し、その板面方向の平均長さが５〜３０μｍであり、厚さ方向の平均長さが０．０５〜０．５μｍであって、かつマグネタイト構造を有することを特徴とする。 That is, the scaly iron oxide particles of the present invention have a scaly shape, the average length in the plate surface direction is 5 to 30 μm, and the average length in the thickness direction is 0.05 to 0.5 μm. And having a magnetite structure.
また、当該鱗片状酸化鉄粒子は、Ｐｂが２０ｐｐｍ以下、Ａｓが５ｐｐｍ以下、Ｈｇが１ｐｐｍ以下、Ｃｄが５ｐｐｍ以下、Ｚｎが１００ｐｐｍ以下、Ｂａが５０ｐｐｍ以下、Ｃｒが１００ｐｐｍ以下、Ｃｕが５０ｐｐｍ以下、およびＮｉが２００ｐｐｍ以下であることが好ましい。 Further, the scaly iron oxide particles, Pb is 20 ppm or less, As is 5 ppm or less, Hg is 1 ppm or less, Cd is 5 ppm or less, Zn is 100 ppm or less, Ba is 50 ppm or less, Cr is 100 ppm or less, Cu is 50 ppm or less, It is preferable that Ni and Ni are 200 ppm or less.
上記の鱗片状酸化鉄粒子は化粧料として好適に使用することができる。 The above scale-like iron oxide particles can be suitably used as a cosmetic.
本発明によるマグネタイト構造を有する鱗片状酸化鉄粒子は、光輝性に優れ、化粧料、塗料、合成樹脂、インキ、合成皮革および抄紙等の各分野に有用である。 The scaly iron oxide particles having a magnetite structure according to the present invention are excellent in glitter and are useful in various fields such as cosmetics, paints, synthetic resins, inks, synthetic leather and papermaking.
本発明の鱗片状酸化鉄粒子は、ヘマタイト構造を有するＡｌ含有鱗片状酸化鉄粒子を還元し、板面方向の平均長さが５〜３０μｍであり、厚さ方向の平均長さが０．０５〜０．５μｍであって、マグネタイト構造としたものである。以下、順に詳しく説明する。 The scaly iron oxide particles of the present invention reduce the Al-containing scaly iron oxide particles having a hematite structure, the average length in the plate surface direction is 5 to 30 μm, and the average length in the thickness direction is 0.05. It is ˜0.5 μm and has a magnetite structure. Hereinafter, it explains in detail in order.
（ヘマタイト構造を有する鱗片状酸化鉄粒子）
ヘマタイト構造を有する鱗片状酸化鉄粒子は、天然品と合成品に大きく分けることができる。天然品は粒径、粒子形状が不揃いで、光輝性に劣るため本用途には適さない。一方、合成品のヘマタイト構造を有する鱗片状酸化鉄粒子は粒径、粒子形状が均一であり、光輝性を求める本用途に好適である。
(Scaly iron oxide particles with hematite structure)
Scale-like iron oxide particles having a hematite structure can be roughly divided into natural products and synthetic products. Natural products are not suitable for this application because they have irregular particle sizes and particle shapes and are inferior in glitter. On the other hand, the scale-like iron oxide particles having a synthetic hematite structure have a uniform particle size and particle shape, and are suitable for the present application for obtaining glitter.
（その合成方法）
ヘマタイト構造を有する鱗片状酸化鉄粒子の合成方法は、文献、特許において公知の技術である。この合成方法を要約すると、ヘマタイト構造を有する鱗片状酸化鉄粒子は、オキシ水酸化鉄を水あるいはアルカリ性の水溶液中において水熱処理をすることによって得ることができる。
(The synthesis method)
A method for synthesizing scaly iron oxide particles having a hematite structure is a known technique in literatures and patents. To summarize this synthesis method, the scaly iron oxide particles having a hematite structure can be obtained by hydrothermal treatment of iron oxyhydroxide in water or an alkaline aqueous solution.
具体的には、オキシ水酸化鉄を水あるいは水酸化ナトリウム、水酸化カリウム、アルミン酸ナトリウム、珪酸ナトリウム等のアルカリ性水溶液に分散懸濁し、懸濁水溶液を圧力容器中１５０〜３００℃で水熱処理することによって、ヘマタイト構造を有する鱗片状酸化鉄粒子を得ることができる。 Specifically, iron oxyhydroxide is dispersed and suspended in water or an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium aluminate or sodium silicate, and the aqueous suspension is hydrothermally treated at 150 to 300 ° C. in a pressure vessel. As a result, scaly iron oxide particles having a hematite structure can be obtained.
一例としては、オキシ水酸化鉄としてチタン工業製 ＴＡＲＯＸ ＨＹ−１００を用い、当該オキシ水酸化鉄１４０ｇをＡｌ２Ｏ３として１４３ｇ／Ｌ、Ｎａ２Ｏとして２１７ｇ／Ｌの濃度のアルミン酸ナトリウム水溶液１Ｌに懸濁して、圧力容器中２７０℃で水熱反応することにより、ヘマタイト構造を有するＡｌ含有鱗片状酸化鉄粒子を得ることができる。 As an example, TAROX HY-100 made by Titanium Industry is used as iron oxyhydroxide, and 140 g of the iron oxyhydroxide is 143 g / L as Al 2 O 3 and 1 L of sodium aluminate aqueous solution with a concentration of 217 g / L as Na 2 O. And the Al-containing flaky iron oxide particles having a hematite structure can be obtained by hydrothermal reaction at 270 ° C. in a pressure vessel.
また、アルカリ性水溶液の種類、濃度等を適宜変更することによって、産物である鱗片状酸化鉄粒子の粒径、粒子形状および当該産物に含有されるＦｅ以外の異種金属元素の種類と含有量を調整することも可能である。 In addition, by appropriately changing the type, concentration, etc. of the alkaline aqueous solution, the particle size and particle shape of the scale-like iron oxide particles as the product and the type and content of the dissimilar metal element other than Fe contained in the product are adjusted. It is also possible to do.
また、前記オキシ水酸化鉄において、有害金属の少ないものを使用することで、外原規２００６（日本）、ＦＤＡ（米国）、およびＥ１７２（欧州）の規制に適応した化粧品原料としての鱗片状酸化鉄粒子とすることも可能である。具体的には、Ｐｂが２０ｐｐｍ以下、Ａｓが５ｐｐｍ以下、Ｈｇが１ｐｐｍ以下、Ｃｄが５ｐｐｍ以下、Ｚｎが１００ｐｐｍ以下、Ｂａが５０ｐｐｍ以下、Ｃｒが１００ｐｐｍ以下、Ｃｕが５０ｐｐｍ以下、およびＮｉが２００ｐｐｍ以下のオキシ水酸化鉄を用いれば、外原規２００６およびＥ１７２に適応する。さらにＰｂが１０ｐｐｍ以下、Ａｓが３ｐｐｍ以下、およびＨｇが３ｐｐｍ以下のオキシ水酸化鉄を用いれば、ＦＤＡにも適応したものを得ることができる。 In addition, the use of iron oxyhydroxide with less harmful metals makes it possible to use flaky oxidation as a cosmetic raw material that complies with the regulations of Tobara 2006 (Japan), FDA (US), and E172 (Europe). Iron particles can also be used. Specifically, Pb is 20 ppm or less, As is 5 ppm or less, Hg is 1 ppm or less, Cd is 5 ppm or less, Zn is 100 ppm or less, Ba is 50 ppm or less, Cr is 100 ppm or less, Cu is 50 ppm or less, and Ni is 200 ppm or less. If this iron oxyhydroxide is used, it conforms to the outer standard 2006 and E172. Further, if iron oxyhydroxide having Pb of 10 ppm or less, As of 3 ppm or less, and Hg of 3 ppm or less is used, a material suitable for FDA can be obtained.
（その寸法）
本発明に用いるヘマタイト構造の鱗片状酸化鉄粒子には上記の合成品であれば、基本的に使用することができるが、光輝性を有するマグネタイト構造の鱗片状酸化鉄粒子を得るには、板面方向の平均長さが５〜３０μｍであり、かつ、厚さ方向の長さが０．０５〜０．５μｍである必要がある。板面方向の平均長さは好ましくは７〜２５μｍであり、厚さ方向の平均長さは好ましくは０．１〜０．４μｍである。両者が上記範囲を外れると光輝性が損なわれて好ましくない。
(Its dimensions)
The hematite-structured scaly iron oxide particles used in the present invention can be basically used as long as they are the above synthetic products. However, in order to obtain magnetite-structured scaly iron oxide particles having glitter, It is necessary that the average length in the plane direction is 5 to 30 μm and the length in the thickness direction is 0.05 to 0.5 μm. The average length in the plate surface direction is preferably 7 to 25 μm, and the average length in the thickness direction is preferably 0.1 to 0.4 μm. If both are out of the above range, the glitter is impaired, which is not preferable.
（還元方法）
ヘマタイト構造の鱗片状酸化鉄粒子からマグネタイト構造を有する鱗片状酸化鉄粒子への還元は、ヘマタイト構造を有する鱗片状酸化鉄粒子を還元雰囲気中で３５０〜６００℃に加熱することにより達成される。３５０℃より低温ではマグネタイト構造に還元されなかったり、あるいはマグネタイト構造を得るのに長時間を要し不経済である。一方、６００℃より高温ではさらに一酸化鉄や鉄まで還元し、鱗片状の形骸が損なわれるので好ましくない。
(Reduction method)
Reduction of the hematite-structured scaly iron oxide particles to the scaly iron oxide particles having a magnetite structure is achieved by heating the scaly iron oxide particles having a hematite structure to 350 to 600 ° C. in a reducing atmosphere. If the temperature is lower than 350 ° C., it is not reduced to a magnetite structure, or it takes a long time to obtain a magnetite structure, which is uneconomical. On the other hand, when the temperature is higher than 600 ° C., iron monoxide and iron are further reduced, and the scale-like shape is damaged, which is not preferable.
還元雰囲気を得るには水素、一酸化炭素、アンモニアのような還元性ガスを用いることの他に、当該温度でこれら還元性ガスと同様の効果を発揮する有機物、例えばコークス、ヤシ油、木片などを使用することも可能である。ただし灰分が多量に残るような有機物では、還元後に灰分を分離する工程が必要となるので好ましくない。 In addition to using reducing gases such as hydrogen, carbon monoxide, and ammonia to obtain a reducing atmosphere, organic substances that exhibit the same effects as these reducing gases at the temperature, such as coke, coconut oil, wood chips, etc. Can also be used. However, an organic substance in which a large amount of ash remains is not preferable because it requires a step of separating the ash after the reduction.
（マグネタイト構造を有する鱗片状酸化鉄粒子の表面改質）
以上により得たマグネタイト構造を有する鱗片状酸化鉄粒子は、光輝性に優れ、化粧料、塗料、合成樹脂、インキ、合成皮革および抄紙等の各分野に有用であるが、さらにその用途によっては表面改質を目的とした表面処理を、光輝性を損なわない範囲で施してもよい。
(Surface modification of scaly iron oxide particles with magnetite structure)
The scaly iron oxide particles having a magnetite structure obtained as described above are excellent in luster and useful in various fields such as cosmetics, paints, synthetic resins, inks, synthetic leather, and papermaking. Surface treatment for the purpose of modification may be performed within a range that does not impair the glitter.
すなわち、シリカ、含水アルミナ、含水酸化チタン等に代表される無機物やオレイン酸、ステアリン酸、アルキルベンゼンスルホン酸等に代表される有機系界面活性剤、シランカップリング剤、チタネートカップリング剤等に代表される無機−有機カップリング剤等を、その目的に応じて、単独あるいは複合して処理した上で用いてもよい。 In other words, it is represented by inorganic substances typified by silica, hydrous alumina, hydrous titanium oxide, etc., organic surfactants typified by oleic acid, stearic acid, alkylbenzene sulfonic acid, etc., silane coupling agents, titanate coupling agents, etc. Depending on the purpose, inorganic-organic coupling agents and the like may be used alone or in combination.
（測定方法等）
本発明の鱗片状酸化鉄粒子の平均長さの測定、およびマグネタイト構造の確認は以下のようにして行った。
(Measurement method, etc.)
Measurement of the average length of the scaly iron oxide particles of the present invention and confirmation of the magnetite structure were performed as follows.
［平均長さ］
板状方向の平均長さは、株式会社島津製作所製レーザー回折式粒度分布測定装置ＳＡＬＤ−２０００を用い、産物を分散した希薄スラリーのレーザー回折−粒度測定法によりメディアン径を測定した。また、厚み方向の平均長さは、適当な倍率で撮影した走査型電子顕微鏡写真から約５０個の粒子の厚みを物差しで計測して、その平均値とした。
[Average length]
The average length in the plate-like direction was measured using a laser diffraction particle size distribution analyzer SALD-2000 manufactured by Shimadzu Corporation, and the median diameter was measured by a laser diffraction particle size measurement method of a diluted slurry in which the product was dispersed. The average length in the thickness direction was determined by measuring the thickness of about 50 particles with a ruler from a scanning electron micrograph taken at an appropriate magnification.
［マグネタイト構造］
産物の構造は、Ｘ線回折装置に株式会社リガク製ＲＩＮＴ２０００＋シリーズ／単独型用／横型／縦型ロータフレックスを用い、ターゲットをＣｕ、ターゲット電圧５０ｋＶ、ターゲット電流２００ｍＡで発生したＣｕＫα線をＸ線源とし、回折角度を２θとして１０〜９０°の範囲で、粉末Ｘ線回折法により得られた回折線チャートを、Ｘ線回折装置付設の電子計算機の定性ソフトウエアーでＪＣＰＤＳカードと照合して確認した。
[Magnetite structure]
The structure of the product is X-ray diffractometer using Rigaku Corporation RINT2000 + series / single type / horizontal / vertical rotor flex, Cu is the target, the target voltage is 50 kV, and the target current is 200 mA. The diffraction line chart obtained by the powder X-ray diffraction method was confirmed by collating with a JCPDS card with the qualitative software of an electronic computer attached to the X-ray diffractometer in the range of 10 to 90 ° with a diffraction angle of 2θ. .
［光輝性］
光輝性は様々な方法が考案されているものの、光輝性顔料は多種多様な用途で様々な形態に加工されて使用されるため、一つの手法をもって一義的に光輝性を決定することは困難である。このため光輝性は、産物を胴径３０ｍｍ、内容積３０ｍＬのガラス瓶に入れ、相互に光輝感を目視観察してその優劣を決定した。「光輝性に特に優れる」を◎、「光輝性に優れる」を○、及び「光輝性に劣る」を×とした。
[Brightness]
Although various methods have been devised for glitter, glitter pigments are processed and used in various forms for a variety of purposes, so it is difficult to uniquely determine glitter with one method. is there. For this reason, the brightness was determined by placing the product in a glass bottle with a body diameter of 30 mm and an internal volume of 30 mL, and visually observing the glitter feeling with each other. “Especially excellent in glitter” was marked with “◎”, “Excellent in glitter” was marked with “◯”, and “Inferior in glitter” was marked with “X”.
また、本発明の鱗片状酸化鉄粒子を化粧品に使用するには、例えば、発明協会公開技報公技番号２００７−５００９０９（発行日２００７．２．１９）に記載されている板状酸化鉄（チタン工業製ＡＭ−２００）を当該鱗片状酸化鉄粒子に置き換えることにより行うことができる。 In addition, in order to use the scaly iron oxide particles of the present invention in cosmetics, for example, plate-like iron oxide described in the Japan Society of Invention and Innovation Technical Bulletin No. 2007-500909 (issue date 2007.2.19) ( It can be performed by replacing AM-200) manufactured by Titanium Industry with the scaly iron oxide particles.
以下に実施例を挙げて本発明をさらに詳細に説明する。以下の実施例は単に例示の為に記すものであり、発明の範囲がこれらによって制限されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. The following examples are given for illustrative purposes only and are not intended to limit the scope of the invention.
［参考例１］
板面方向の平均長さ１２μｍのヘマタイト構造を有する鱗片状酸化鉄を水素雰囲気下、５００℃で１ｈ還元し、板面方向の平均長さ１４μｍ、厚み方向の平均長さ０．４μｍのマグネタイト構造を有する鱗片状酸化鉄を得た。この産物の光輝性は○であった。
[ Reference Example 1 ]
A scale-like iron oxide having a hematite structure with an average length of 12 μm in the plate surface direction is reduced at 500 ° C. for 1 h in a hydrogen atmosphere, and a magnetite structure with an average length of 14 μm in the plate surface direction and an average length of 0.4 μm in the thickness direction. A scaly iron oxide having the following was obtained. The brightness of this product was good.
［参考例２］
板面方向の平均長さ２１μｍ、厚み方向の平均長さ０．５μｍのヘマタイト構造を有する鱗片状酸化鉄を水素雰囲気下、５５０℃で１ｈ還元し、板面方向の平均長さ２６μｍ、厚み方向の平均長さ０．５μｍのマグネタイト構造を有する鱗片状酸化鉄を得た。この産物の光輝性は○であった。
[ Reference Example 2 ]
Scale-like iron oxide having a hematite structure with an average length in the plate surface direction of 21 μm and an average length in the thickness direction of 0.5 μm was reduced at 550 ° C. for 1 h in a hydrogen atmosphere, and the average length in the plate surface direction was 26 μm and the thickness direction A scaly iron oxide having a magnetite structure with an average length of 0.5 μm was obtained. The brightness of this product was good.
［実施例１］
板面方向の平均長さ１２μｍ、厚み方向の平均長さ０．２μｍのヘマタイト構造を有するＡｌ含有鱗片状酸化鉄を水素雰囲気下、５００℃で１ｈ還元し、板面方向の平均長さ１４μｍ、厚み方向の平均長さ０．２μｍのマグネタイト構造を有する鱗片状酸化鉄を得た。この産物の光輝性は◎であった。
[ Example 1 ]
Al-containing flaky iron oxide having a hematite structure with an average length in the plate surface direction of 12 μm and an average length in the thickness direction of 0.2 μm was reduced at 500 ° C. for 1 h in a hydrogen atmosphere, and the average length in the plate surface direction was 14 μm. A scaly iron oxide having a magnetite structure with an average length in the thickness direction of 0.2 μm was obtained. The brightness of this product was ◎.
［実施例２］
板面方向の平均長さ５μｍ、厚み方向の平均長さ０．１μｍのヘマタイト構造を有するＡｌ含有鱗片状酸化鉄を一酸化炭素雰囲気下、４５０℃で１ｈ還元し、板面方向の平均長さ７μｍ、厚み方向の平均長さ０．１μｍのマグネタイト構造を有する鱗片状酸化鉄を得た。この産物の光輝性は○であった。
[ Example 2 ]
Al-containing flaky iron oxide having a hematite structure with an average length in the plate surface direction of 5 μm and an average length in the thickness direction of 0.1 μm is reduced at 450 ° C. for 1 h in a carbon monoxide atmosphere, and the average length in the plate surface direction A scaly iron oxide having a magnetite structure of 7 μm and an average length in the thickness direction of 0.1 μm was obtained. The brightness of this product was good.
［実施例３］
板面方向の平均長さ１８μｍのヘマタイト構造を有するＡｌ含有鱗片状酸化鉄を水素雰囲気下、５５０℃で１ｈ還元し、板面方向の平均長さ２２μｍ、厚み方向の平均長さ０．２μｍのマグネタイト構造を有する鱗片状酸化鉄を得た。この産物の光輝性は◎であった。
[ Example 3 ]
An Al-containing flaky iron oxide having a hematite structure with an average length of 18 μm in the plate surface direction is reduced at 550 ° C. for 1 h in a hydrogen atmosphere, an average length of 22 μm in the plate surface direction, and an average length of 0.2 μm in the thickness direction. A scaly iron oxide having a magnetite structure was obtained. The brightness of this product was ◎.
［実施例４］
板面方向の平均長さ１２μｍ、厚み方向の平均長さ０．２μｍのヘマタイト構造を有するＡｌ、Ｚｎ含有鱗片状酸化鉄をヤシ油を用いて、５００℃で３ｈ還元し、板面方向の平均長さ１３μｍ、厚み方向の平均長さ０．２μｍのマグネタイト構造を有する鱗片状酸化鉄を得た。この産物の光輝性は○であった。
[ Example 4 ]
Al-Zn-containing flaky iron oxide having a hematite structure with an average length in the plate surface direction of 12 μm and an average length in the thickness direction of 0.2 μm was reduced using palm oil at 500 ° C. for 3 hours, and the average in the plate surface direction A scaly iron oxide having a magnetite structure having a length of 13 μm and an average length in the thickness direction of 0.2 μm was obtained. The brightness of this product was good.
［実施例５］
板面方向の平均長さ５μｍ、厚み方向の平均長さ０．１μｍのヘマタイト構造を有するＡｌ、Ｓｉ含有鱗片状酸化鉄を水素雰囲気下、５００℃で２ｈ還元し、板面方向の平均長さ６μｍ、厚み方向の平均長さ０．１μｍのマグネタイト構造を有する鱗片状酸化鉄を得た。この産物の光輝性は○であった。
[ Example 5 ]
Al and Si-containing flaky iron oxide having a hematite structure with an average length of 5 μm in the plate surface direction and an average length of 0.1 μm in the thickness direction is reduced at 500 ° C. for 2 hours in a hydrogen atmosphere, and the average length in the plate surface direction A scaly iron oxide having a magnetite structure of 6 μm and an average length in the thickness direction of 0.1 μm was obtained. The brightness of this product was good.
［実施例６］
高純度のオキシ水酸化鉄、すなわちＰｂが１ｐｐｍ未満、Ａｓが１ｐｐｍ未満、Ｈｇが１ｐｐｍ未満、Ｃｄが１ｐｐｍ未満、Ｚｎが６ｐｐｍ、Ｂａが２ｐｐｍ未満、Ｃｒが７ｐｐｍ、Ｃｕが６ｐｐｍ、およびＮｉが２ｐｐｍの含有量であるオキシ水酸化鉄を原料とした、板面方向の平均長さ１５μｍ、厚み方向の平均長さ０．２μｍのヘマタイト構造を有するＡｌ含有鱗片状酸化鉄を水素雰囲気下、５００℃で１ｈ還元し、板面方向の平均長さ１８μｍ、厚み方向の平均長さ０．２μｍのマグネタイト構造を有する鱗片状酸化鉄を得た。このものは光輝性に優れるものであった。図１に、この鱗片状酸化鉄粒子の走査型電子顕微鏡写真（倍率１，０００倍）を示す。
[ Example 6 ]
High purity iron oxyhydroxide, ie, Pb less than 1 ppm, As less than 1 ppm, Hg less than 1 ppm, Cd less than 1 ppm, Zn less than 6 ppm, Ba less than 2 ppm, Cr 7 ppm, Cu 6 ppm, and Ni 2 ppm Al-containing flaky iron oxide having a hematite structure with an average length in the plate surface direction of 15 μm and an average length in the thickness direction of 0.2 μm, using iron oxyhydroxide as a raw material at 500 ° C. in a hydrogen atmosphere To obtain a scaly iron oxide having a magnetite structure with an average length of 18 μm in the plate surface direction and an average length of 0.2 μm in the thickness direction. This was excellent in glitter. FIG. 1 shows a scanning electron micrograph (1,000 times magnification) of the scaly iron oxide particles.
また、当該産物中の不純物含有量はＰｂが１ｐｐｍ、Ａｓが１ｐｐｍ未満、Ｈｇが１ｐｐｍ未満、Ｃｄが１ｐｐｍ未満、Ｚｎが３ｐｐｍ、Ｂａが２ｐｐｍ未満、Ｃｒが１７ｐｐｍ、Ｃｕが５ｐｐｍ、およびＮｉが１０ｐｐｍであり、外原規２００６（日本）、ＦＤＡ（米国）、およびＥ１７２（欧州）の規制に適応した化粧品原料として好適な鱗片状酸化鉄粒子であった。この産物の光輝性は◎であった。 Also, the impurity content in the product is 1 ppm for Pb, less than 1 ppm for As, less than 1 ppm for Hg, less than 1 ppm for Cd, 3 ppm for Zn, less than 2 ppm for Ba, 17 ppm for Cr, 5 ppm for Cu, and 10 ppm for Ni It was a scaly iron oxide particle suitable as a cosmetic raw material adapted to the regulations of Sotobara 2006 (Japan), FDA (USA), and E172 (Europe). The brightness of this product was ◎.
［比較例１］
板面方向の平均長さ２μｍ、厚み方向の平均長さ０．０３μｍのヘマタイト構造を有する鱗片状酸化鉄を水素雰囲気下、４５０℃で１ｈ還元し、板面方向の平均長さ３μｍ、厚み方向の平均長さ０．０３μｍのマグネタイト構造を有する鱗片状酸化鉄を得た。この産物の光輝性は×であった。
[Comparative Example 1]
Scale-like iron oxide having a hematite structure with an average length of 2 μm in the plate surface direction and an average length of 0.03 μm in the thickness direction was reduced at 450 ° C. for 1 h in a hydrogen atmosphere, and the average length in the plate surface direction was 3 μm. A scaly iron oxide having a magnetite structure with an average length of 0.03 μm was obtained. The brightness of this product was x.
［比較例２］
板面方向の平均長さ５０μｍ、厚み方向の平均長さ０．７μｍのヘマタイト構造を有する鱗片状酸化鉄を水素雰囲気下、６００℃で３ｈ還元し、板面方向の平均長さ５２μｍ、厚み方向の平均長さ０．７μｍのマグネタイト構造を有する鱗片状酸化鉄を得た。この産物の光輝性は×であった。
[Comparative Example 2]
Scale-like iron oxide having a hematite structure with an average length in the plate surface direction of 50 μm and an average length in the thickness direction of 0.7 μm was reduced at 600 ° C. for 3 hours in a hydrogen atmosphere, and the average length in the plate surface direction was 52 μm and the thickness direction A scaly iron oxide having a magnetite structure with an average length of 0.7 μm was obtained. The brightness of this product was x.
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| JP2022177647A (en) * | 2021-05-18 | 2022-12-01 | チタン工業株式会社 | Iron oxide pigment for cosmetic composition and cosmetic composition containing iron oxide pigment |
| KR20240016429A (en) | 2021-06-08 | 2024-02-06 | 로레알 | Make-up composition containing a flake-type aluminum pigment and a flake-type black pigment |
| FR3124699B1 (en) | 2021-07-05 | 2024-04-26 | Oreal | COMPOSITION FOR MAKE-UP, COMPRISING GLITTER-TYPE ALUMINUM PIGMENTS AND GLITTER-TYPE BLACK PIGMENTS |
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| US4373963A (en) * | 1981-09-03 | 1983-02-15 | Titan Kogyo K.K. | Lustrous pigment and process for producing same |
| DE3636076A1 (en) * | 1986-10-23 | 1988-04-28 | Merck Patent Gmbh | PLATE-SHAPED IRON OXIDE PIGMENTS |
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| JP3942963B2 (en) * | 2002-06-28 | 2007-07-11 | ケミライト工業株式会社 | Plate-like iron oxyhydroxide, iron oxide, magnetite as a secondary structure and production method thereof |
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