JP2007063127A - Mica-based composite material and its producing method - Google Patents
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Abstract
Description
本発明は雲母系複合材料およびその製造方法、特に光学的性質に優れた雲母系複合材料に関する。 The present invention relates to a mica-based composite material and a method for producing the same, and more particularly to a mica-based composite material having excellent optical properties.
化粧料あるいは塗料など、特殊な意匠性が要求される分野においては、顔料などの粉体にも単に特定の色を求めるだけでなく、光輝性あるいは見る角度により色調ないし干渉色などの変化する多色フリップ・フロップ効果等を有した粉体の需要が増大している。これらの要求を満たすものとして、従来より雲母の表面を二酸化チタンや酸化鉄で被覆した雲母系複合材料あるいは該雲母系複合材料にさらに群青や紺青、カーミン、コバルト酸化物、ジルコニウム酸化物、アルミニウム酸化物、珪素酸化物、リチウム酸化物、ニッケル酸化物などの一種又は二種以上を被覆したものが知られている。これらの雲母系複合材料は、真珠光沢顔料として種々の干渉色を有することから、化粧料、塗料、プラスチックなどの顔料として広く用いられていた。 In fields where special design properties are required, such as cosmetics and paints, not only a specific color is required for powders such as pigments, but also the color tone or interference color changes depending on the brightness or viewing angle. There is an increasing demand for powders having a color flip-flop effect. In order to satisfy these requirements, a mica-based composite material in which the surface of mica has been coated with titanium dioxide or iron oxide or the mica-based composite material is further added to ultramarine, bitumen, carmine, cobalt oxide, zirconium oxide, aluminum oxide. A material coated with one or more of silicon oxide, lithium oxide, nickel oxide and the like is known. Since these mica-based composite materials have various interference colors as pearlescent pigments, they have been widely used as pigments for cosmetics, paints, plastics and the like.
しかしながら、従来の雲母系複合材料は、粒子の板径が大きいものでも０．０８ｍｍ（８０μｍ）以下であるために、その塗布面はほぼ均一なものとして看取され、きらきらと輝いた干渉色の強い光輝性や多色性フリップフロップ効果を発現することはできず、意匠性の弱い雲母系複合材料であった。
一方、特開平６−９３２０５号公報には、粒径が０．１〜５ｍｍの雲母表面に一種以上の金属酸化物微粒子を前記雲母に対し０．１〜１５重量％被覆し、配向させなくともどの角度から見ても光輝感を発現し得る装飾用顔料が開示されている。
However, since the conventional mica-based composite material has a particle diameter of 0.08 mm (80 μm) or less even when the particle diameter is large, the coated surface is considered to be almost uniform, and the interference color that is brilliantly shining is obtained. It was a mica-based composite material that could not exhibit strong luster and pleochroic flip-flop effect and had poor design.
On the other hand, JP-A-6-93205 discloses that a mica surface having a particle diameter of 0.1 to 5 mm is coated with 0.1 to 15% by weight of one or more metal oxide fine particles with respect to the mica and not oriented. A decorative pigment is disclosed that can exhibit a brilliant feeling when viewed from any angle.
しかし、この顔料は配向させなくてもどの角度から見ても光輝感を発現させるため、核雲母を厚い立方体形状にすることが必要であり、多色性フリップフロップ効果は全く発現されないものであった。
本発明は前記従来技術の課題に鑑みなされたものであり、その目的は光輝感に優れしかも多色性フリップフロップ効果を発現し得る雲母系複合材料を提供することにある。 The present invention has been made in view of the above-mentioned problems of the prior art, and an object thereof is to provide a mica-based composite material that is excellent in glitter and can exhibit a polychromatic flip-flop effect.
前記目的を達成するために本発明者らが鋭意検討を行った結果、薄片状の大粒径雲母に金属酸化物ないし金属水酸化物を被覆することにより、優れた光輝性及び多色性フリップフロップ効果が得られることを見いだし、本発明を完成するに至った。
すなわち、本発明にかかる雲母系複合材料は、粒子の板径が０．１ｍｍ以上０．５ｍｍ未満で、粒子の厚さが０．２〜２μｍである大粒径薄片状雲母と、
As a result of intensive studies by the present inventors in order to achieve the above object, excellent glitter and pleochroic flip-flops are obtained by coating flaky large particle mica with metal oxide or metal hydroxide. The present invention has been completed.
That is, the mica-based composite material according to the present invention has a large particle size flaky mica having a particle diameter of 0.1 mm or more and less than 0.5 mm and a particle thickness of 0.2 to 2 μm,
該雲母表面に形成された金属酸化物および／又は金属水酸化物の一種又は二種以上からなる被覆層と、からなり、
金属酸化物が二酸化チタンを含む場合は二酸化チタンはルチル型及び／又はアナターゼ型であることを特徴とする。
また、本発明にかかる材料において、雲母が合成雲母であることが好適である。
A coating layer made of one or more metal oxides and / or metal hydroxides formed on the mica surface;
When the metal oxide contains titanium dioxide, the titanium dioxide is a rutile type and / or anatase type.
In the material according to the present invention, it is preferable that the mica is synthetic mica.
また、本発明にかかる材料において、前記金属酸化物ないし金属水酸化物における金属は、チタン、鉄、亜鉛、ジルコニウム、コバルト、ニッケル、リチウム、ナトリウム、珪素、アルミニウム、ビスマス、タングステン、スズからなる群より選択される一種又は二種以上であることが好適である。
また、本発明にかかる材料において、前記金属酸化物ないし金属水酸化物の一種又は二種以上の被覆量は、大粒径薄片状雲母に対し、０．１〜５０重量％であることが好適である。
また、本発明にかかる製造方法は、大粒径薄片状雲母に金属酸化物及び／又は金属水酸化物の一種又は二種以上を被覆した後、２００〜１２００℃で焼成することを特徴とする。
Further, in the material according to the present invention, the metal in the metal oxide or metal hydroxide is a group consisting of titanium, iron, zinc, zirconium, cobalt, nickel, lithium, sodium, silicon, aluminum, bismuth, tungsten, tin. It is suitable that it is 1 type selected from 2 or more types.
Further, in the material according to the present invention, the coating amount of one or more of the metal oxide or metal hydroxide is preferably 0.1 to 50% by weight with respect to the large particle size flaky mica. It is.
In addition, the production method according to the present invention is characterized in that a large particle size flaky mica is coated with one or more metal oxides and / or metal hydroxides and then fired at 200 to 1200 ° C. .
本発明にかかる雲母系複合材料によれば、大粒径薄片状雲母に金属酸化物および／又は金属水酸化物を被覆することとしたので、光輝性とともに、優れた多色性フリップフロップ効果を発揮することができる。
また、本発明にかかる雲母系複合材料の製造方法によれば、大粒径薄片状雲母に金属酸化物ないし金属水酸化物を被覆した後、焼成することとしたので、光輝性及び多色性フリップフロップ効果をより顕著に発揮することができる。
According to the mica-based composite material according to the present invention, the large particle size flaky mica is coated with the metal oxide and / or metal hydroxide. It can be demonstrated.
In addition, according to the method for producing a mica-based composite material according to the present invention, a large particle size flaky mica is coated with a metal oxide or a metal hydroxide, and then fired. The flip-flop effect can be exhibited more remarkably.
以下、本発明の好適な実施形態について説明する。
本発明において好適に用いられる大粒径薄片状雲母は、天然雲母であっても合成雲母であっても差し支えないが、天然雲母は不純物を含んでいるため大粒径薄片状雲母の粒子の透明性が若干低下する。この点で不純物が少なく透明度及び白色度の高い合成雲母が好ましい。また、天然雲母を用いる場合には、透明度を上げるために塩酸や硝酸の水溶液で洗浄することが好ましい。
大粒径薄片状雲母の製造工程の例を以下に示す。
Hereinafter, preferred embodiments of the present invention will be described.
The large particle size flaky mica preferably used in the present invention may be natural mica or synthetic mica, but since natural mica contains impurities, the particles of the large particle flaky mica are transparent. The characteristics are slightly reduced. In this respect, synthetic mica having less impurities and high transparency and whiteness is preferable. When natural mica is used, it is preferably washed with an aqueous solution of hydrochloric acid or nitric acid in order to increase transparency.
An example of the production process of large particle size flaky mica is shown below.
大粒径薄片状雲母を天然雲母より得るには、まず採掘した原鉱石雲母をクラッシャーで粗粉砕し、約２０ｍｍ前後の不定形粗粉とする。これを７５０〜８００℃で約２時間、大気中で焼成した。放冷後、雲母を薄片化するために、希薄塩酸水溶液に懸濁させスラリー状態とした。一昼夜放置後、これに炭酸ナトリウムを加えて層間を開き、劈開しやすくした。スラリーの状態で湿式にてスリップ解砕した。解砕は１２時間行い、これに水を加えて２０メッシュの篩を通過させる。通過した湿式解砕物を２００メッシュの篩を通し、未通過物を回収し、これにさらに水を加えて２００メッシュの篩を通し、微粒子を通過させた。この工程を３回繰り返し、微粒子を十分に除去した。また、２０メッシュの篩に残った未通過物は再度湿式解砕を１２時間行い、上述と同様な工程で処理した。解砕後に篩分級し、回収した天然雲母は、水分が約３０％になるまで濾過した。さらに白色度を上げるために３０％含水している解砕天然雲母１Ｋｇに０．２Ｎ硝酸水溶液１Ｌを加えた。これにクエン酸５０ｇを加えてプロペラ攪拌を１日行った。濾過・水洗後８０℃以下の低温度で乾燥した。乾燥物は低速のヘンシェルミキサーにて凝集状態をほぐして大粒径薄片状天然雲母６５０ｇを得た。 In order to obtain a large particle size flaky mica from natural mica, first, the mined raw ore mica is roughly pulverized with a crusher to obtain an irregular coarse powder of about 20 mm. This was calcined in the atmosphere at 750 to 800 ° C. for about 2 hours. After cooling, in order to flake the mica, it was suspended in a dilute hydrochloric acid aqueous solution to form a slurry. After standing for a whole day and night, sodium carbonate was added thereto to open the layers, making it easy to cleave. Slip pulverization was performed in a wet state in a slurry state. Crushing is carried out for 12 hours, and water is added to this and passed through a 20-mesh sieve. The passed wet pulverized product was passed through a 200-mesh sieve, and the non-passed product was collected. Water was further added to this and passed through the 200-mesh sieve to allow fine particles to pass through. This process was repeated three times to sufficiently remove the fine particles. In addition, the non-passed matter remaining on the 20 mesh sieve was again subjected to wet crushing for 12 hours and processed in the same process as described above. The pulverized natural mica after pulverization was filtered until the water content was about 30%. In order to further increase the whiteness, 1 L of a 0.2N nitric acid aqueous solution was added to 1 kg of crushed natural mica containing 30% water. To this was added 50 g of citric acid, and propeller stirring was performed for 1 day. After filtration and washing with water, it was dried at a low temperature of 80 ° C. or lower. The dried product was flocculated with a low-speed Henschel mixer to obtain 650 g of flake natural mica having a large particle size.
大粒径薄片状雲母を合成雲母より得る例として、合成フッ素雲母を用いる例について説明する。合成フッ素金雲母の化学式はＫＭｇ３（ＡｌＳｉ３Ｏ１０）Ｆ２である。溶融析出法で製造する場合、例えばＳｉＯ２を１８００ｇ，Ａｌ２Ｏ３を５１０ｇ，Ｋ２ＣＯ３を６９０ｇ、ＭｇＦ２を６３０ｇ秤り取り、Ｖ型ブレンダーにて十分混合した。混合物を１５００℃に加熱し、溶融状態にした後、薄片状大粒径の合成雲母を得るために、溶融状態から１３００℃まで冷却させる。この際の冷却速度を１００℃／１５時間とした。さらに１３００℃で２４時間放置した。この後、室温に３日間放置して冷却した。このようにして結晶性のよい合成雲母を得、これを２０ｍｍぐらいになるように粗粉砕した。これに水を加えて大粒径薄片状天然雲母を得たのと同様な工程で解砕、篩い分け、乾燥した。乾燥物をほぐして大粒径薄片状合成フッ素金雲母１０００ｇを得た。 As an example of obtaining large particle size flaky mica from synthetic mica, an example using synthetic fluorine mica will be described. The chemical formula of the synthetic fluorine phlogopite is KMg 3 (AlSi 3 O 10 ) F 2 . When producing a melt deposition method, for example, a SiO 2 1800 g, 510 g of Al 2 O 3, 690 g of K 2 CO 3, MgF 2 and 630g weighed and thoroughly mixed in a V-blender. The mixture is heated to 1500 ° C. and brought into a molten state, and then cooled from the molten state to 1300 ° C. in order to obtain a flaky large particle size synthetic mica. The cooling rate at this time was 100 ° C./15 hours. Further, it was left at 1300 ° C. for 24 hours. Thereafter, it was allowed to cool at room temperature for 3 days. Thus, synthetic mica having good crystallinity was obtained, and this was coarsely pulverized to about 20 mm. This was crushed, sieved and dried in the same process as adding water to obtain flaky natural mica with a large particle size. The dried product was loosened to obtain 1000 g of a large particle size flaky synthetic fluorine phlogopite.
上記のように大粒径薄片状雲母は篩分級法により製造したが、粒子の厚さは走査型電子顕微鏡で観察して得た。
本発明にかかる雲母系複合材料は上述した製造法によって得た大粒径薄片状雲母を核とし、該核雲母粒子の表面が金属酸化物及び／又は金属水酸化物の一種または二種以上で被覆されている。これらの該金属酸化物及び／又は金属水酸化物の金属は、チタン、鉄、亜鉛、ジルコニウム、コバルト、ニッケル、リチウム、ナトリウム、ケイ素、アルミニウム、ビスマス、タングステン、スズより選択される。そして、金属酸化物及び／又は金属水酸化物の一種または二種以上による被覆量は大粒径薄片状雲母に対して０．１〜５０重量％である。さらに金属酸化物及び／又は金属水酸化物の一種または二種以上で被覆した大粒径薄片状雲母は２００〜１２００℃、好ましくは５００〜１１００℃で焼成し雲母系複合材料を得ることが好ましい。金属酸化物及び／又は金属水酸化物の被覆量が０．１重量％以下では得られた雲母系複合材料の高彩色とぎらぎらと輝いた干渉色が得られず、光輝性に乏しく、多色性フリップフロップ効果の発現も乏しい。また、５０重量％を越えると、着色性は有するものの粒子の厚さが２μｍ以上になるため、側面の反射が強くなり、ギラギラと輝いた干渉色が弱くなり、光輝性、さらには多色性フリップフロップ効果が乏しく、意匠性にも欠け好ましくない。また、金属酸化物及び／又は金属水酸化物の一種または二種以上で被覆した雲母系複合材料において、２００℃未満の温度で焼成して得られた雲母系複合材料は着色が少なく、しかも多色性フリップフロップ効果の発現にも非常に乏しく意匠性にも欠けていた。さらに、被覆状態より、１２００℃を越える温度で焼成して得られた雲母系複合材料は、被覆物が凝集すると同時に被覆した雲母系複合材料の凝集も起こり、ギラギラと輝いた干渉色が得られず光輝性にも乏しく、多色性フリップフロップ効果の発現も乏しく意匠性に劣り好ましくない。
As described above, the large particle size flaky mica was produced by the sieve classification method, and the thickness of the particles was obtained by observing with a scanning electron microscope.
The mica-based composite material according to the present invention has a large particle size flaky mica obtained by the above-described production method as a nucleus, and the surface of the nuclei mica particle is one or more of metal oxide and / or metal hydroxide. It is covered. The metal of the metal oxide and / or metal hydroxide is selected from titanium, iron, zinc, zirconium, cobalt, nickel, lithium, sodium, silicon, aluminum, bismuth, tungsten, and tin. And the coating amount by 1 type, or 2 or more types of a metal oxide and / or a metal hydroxide is 0.1 to 50 weight% with respect to a large particle size flaky mica. Furthermore, the large particle size flaky mica coated with one or more metal oxides and / or metal hydroxides is preferably fired at 200 to 1200 ° C., preferably 500 to 1100 ° C., to obtain a mica-based composite material. . When the coating amount of the metal oxide and / or metal hydroxide is 0.1% by weight or less, the obtained mica-based composite material cannot provide a high-colored and brilliant interference color, has poor glitter, and is multicolored. The effect of the flip-flop effect is poor. On the other hand, if it exceeds 50% by weight, although the color has a coloring property, the thickness of the particle becomes 2 μm or more, so that the reflection on the side surface becomes strong, the shining interference color becomes weak, the glittering property, and the pleochroicity. The flip-flop effect is poor, and the design is lacking. Further, in the mica-based composite material coated with one or more metal oxides and / or metal hydroxides, the mica-based composite material obtained by firing at a temperature of less than 200 ° C. is less colored and moreover. The color flip-flop effect was very poor and the design was lacking. Furthermore, the mica-based composite material obtained by firing at a temperature exceeding 1200 ° C. from the coated state causes the coating to agglomerate and at the same time agglomeration of the coated mica-based composite material occurs, and a brilliant interference color is obtained. Further, it is not preferable because it has poor glitter and poor polychromatic flip-flop effect and poor design.
本発明の上記雲母系複合材料は大粒径薄片状雲母表面が、好ましくはチタン、鉄、亜鉛、ジルコニウム、コバルト、ニッケル、リチウム、ナトリウム、ケイ素、アルミニウム、ビスマス、タングステン、スズの金属酸化物及び／又は金属水酸化物の一種または二種以上で被覆されてなるものであるが、これを得るには種々の方法を採用することができる。その製法として、真空蒸着被覆法もあるが、特公昭４３−２５６４４号公報に見られるような可溶性無機塩、例えば塩化物、硫酸化物、硝酸化物、炭酸化物、水酸化物などの水溶液を大粒径薄片状雲母の存在下で加水分解し、大粒径薄片状雲母の表面に金属酸化物及び／又は金属水酸化物を析出させた後加熱する方法によって大粒径薄片状雲母系複合材料が得られる。 The mica-based composite material of the present invention has a large particle size flaky mica surface, preferably a metal oxide of titanium, iron, zinc, zirconium, cobalt, nickel, lithium, sodium, silicon, aluminum, bismuth, tungsten, tin, and Although it is a thing coat | covered with 1 type, or 2 or more types of a metal hydroxide, various methods are employable in order to obtain this. As its production method, there is a vacuum deposition coating method, but a soluble inorganic salt such as that disclosed in Japanese Patent Publication No. 43-25644, for example, an aqueous solution of chloride, sulfate, nitrate, carbonate, hydroxide, etc. The large particle size flaky mica-based composite material is hydrolyzed in the presence of the diameter flaky mica and the metal oxide and / or metal hydroxide is precipitated on the surface of the large particle size flaky mica and then heated. can get.
本発明の大粒径薄片状雲母系複合材料は、高彩色のギラギラと輝いた干渉色の強い光輝性及び多色性フリップフロップ効果を発現する意匠性の高い雲母系複合材料である。
しかも、耐光性、耐熱性などの安定性に優れ、塗料、化粧品、プラスチック、インキ、絵の具、装飾品、日用雑貨、繊維製品、セラミックスなどの粉体、着色パール光沢材料として有用であり、意匠性の高い材料として期待される。
The large particle size flaky mica-based composite material of the present invention is a highly designed mica-based composite material that exhibits a high chromatic glitter and a strong brilliant interference color and a polychromatic flip-flop effect.
In addition, it has excellent stability such as light resistance and heat resistance, and is useful as a powder, colored pearl luster material for paints, cosmetics, plastics, inks, paints, ornaments, household goods, textiles, ceramics, etc. It is expected as a highly functional material.
以下、実施例に基づき本発明をより詳細に説明する。なお、本発明はこれらの実施例に限定されるものではない。
実施例１
大粒径薄片状天然雲母１００ｇ（平均粒径約０．５ｍｍ、平均粒子厚約１μｍをイオン交換水１ｌに添加してプロペラにて十分に攪拌し均一に分散させた。得られた分散液に濃度４０重量％の硫酸チタニル水溶液１０２ｍｌを加えて攪拌しながら加熱し３時間沸騰させた。放冷後濾過水洗し１００℃で乾燥させた。乾燥後７００℃で２時間焼成し放冷して銀色の大粒径薄片状天然雲母１１２ｇを得た。得られた大粒径薄片状天然雲母をＸ線回折と走査型電子顕微鏡にて解析した結果、二酸化チタンのアナターゼ型で被覆された大粒径薄片状天然雲母複合材料であった。また、二酸化チタンの被覆量は蛍光Ｘ線分析で定量した。その結果、二酸化チタンの被覆量は１４重量％であった。
次に各種粉体と実施例１記載の粉体との比較結果を示す。
Hereinafter, based on an Example, this invention is demonstrated in detail. The present invention is not limited to these examples.
Example 1
Large particle size flaky natural mica 100 g (average particle size of about 0.5 mm, average particle thickness of about 1 μm was added to 1 liter of ion-exchanged water and stirred well with a propeller to disperse uniformly. After adding 102 ml of titanyl sulfate aqueous solution with a concentration of 40% by weight and heating with stirring, it was boiled for 3 hours. As a result of analyzing the obtained large particle size flaky natural mica by X-ray diffraction and a scanning electron microscope, a large particle size coated with titanium dioxide anatase type was obtained. The coating amount of titanium dioxide was determined by fluorescent X-ray analysis, and as a result, the coating amount of titanium dioxide was 14% by weight.
Next, comparison results between various powders and the powders described in Example 1 are shown.
（表１）
────────────────────────────────────
試 験 例
１ ２ ３ ４ ５
────────────────────────────────────
パール剤 ○ − − − −
大粒径薄片状雲母系複合材料 − ○ − − −
（実施例１）
大粒径シリカ − − ○ − −
大粒径球状樹脂粉末 − − − ○ −
大粒径サイコロ状雲母系複合材料 − − − − ○
────────────────────────────────────
評価項目
キラキラした輝き △ ◎ × × ○
フリップフロップ性 ○ ◎ × × ×
────────────────────────────────────
パール剤：平均５０μｍ径 厚さ０．２μｍ
大径薄片状（合成金）雲母系複合材料：平均１ｍｍ径 厚さ１μｍ
大径シリカ、大径球状樹脂（スチレン）粉末：平均１ｍｍ径
大粒径サイコロ状雲母：平均粒径約０．５ｍｍ 平均粒子厚約２００μｍ
二酸化チタン被覆量１０％
(Table 1)
────────────────────────────────────
Test example
1 2 3 4 5
────────────────────────────────────
Pearl agent ○ − − − −
Large particle size flaky mica based composite material − ○ − − −
Example 1
Large particle size silica--○--
Large particle size spherical resin powder − − − ○ −
Large particle dice mica based composite material----○
────────────────────────────────────
Evaluation item Glittering △ ◎ × × ○
Flip flop ○ ◎ × × ×
────────────────────────────────────
Pearl agent: average 50μm diameter, thickness 0.2μm
Large-diameter flaky (synthetic gold) mica-based composite material: Average 1 mm diameter Thickness 1 μm
Large diameter silica, large diameter spherical resin (styrene) powder: average 1 mm diameter large particle size dice mica: average particle size about 0.5 mm average particle thickness about 200 μm
Titanium dioxide coverage 10%
＜結果＞
上記表１より明らかなように、通常用いられているパール剤の場合（試験例１）には、若干キラキラした輝きを発揮するものの、未だ十分ではない。しかしながら、大粒径薄片状雲母径複合材料の場合（試験例２）には、パール剤を用いた場合よりも遥かにキラキラした輝き及び見る方向により異なる色調を呈するフリップフロップ性が観察され、優れた意匠性を発揮する。
<Result>
As is clear from Table 1 above, in the case of a commonly used pearl agent (Test Example 1), although a slight sparkle is exhibited, it is still not sufficient. However, in the case of a large particle size flaky mica diameter composite material (Test Example 2), the flip-flop property exhibiting a far more brilliant brightness and a different color tone depending on the viewing direction is observed, which is superior to the case of using a pearl agent. Demonstrate its design.
また、他の粉末で大粒径薄片状雲母系複合材料と近似した径の粉末を用いた場合（試験例３，４）には、キラキラした輝きは発揮されず、無論、フリップフロップ性も観察されなかった。
一方、大粒サイコロ状雲母系複合材料（試験例５）は、キラキラして輝きはある程度発揮し、かつ見る方向にかかわらず光輝感は有するものの、特に多色性フリップフロップ効果については全く観察されなかった。
In addition, when a powder having a diameter close to that of a large particle size flaky mica-based composite material is used (Test Examples 3 and 4), the glittering shine is not exhibited, and, of course, the flip-flop property is also observed. Was not.
On the other hand, the large dice mica-based composite material (Test Example 5) is sparkling and exhibits a certain degree of brightness, and has a glittering feeling regardless of the viewing direction, but in particular, no polychromatic flip-flop effect is observed. It was.
次に、本発明者らは雲母の粒径について検討を進めた。
（表２）
────────────────────────────────────
試 験 例
６ ７ ８ ９ １０ １１ １２
────────────────────────────────────
雲母（平均粒径約０．０５ｍｍ） ○ − − − − − −
（平均粒径約０．１ｍｍ） − ○ − − − − −
（平均粒径約０．５ｍｍ） − − ○ − − − −
（平均粒径約１．０ｍｍ） − − − ○ − − −
（平均粒径約１．５ｍｍ） − − − − ○ − −
（平均粒径約２．０ｍｍ） − − − − − ○ −
（平均粒径約３．０ｍｍ） − − − − − − ○
────────────────────────────────────
評価項目
キラキラした輝き △ ○ ◎ ◎ ◎ ◎ ◎
フリップフロップ性 ○ ○ ◎ ◎ ◎ ◎ ◎
────────────────────────────────────
Next, the present inventors proceeded with studies on the particle size of mica.
(Table 2)
────────────────────────────────────
Test example
6 7 8 9 10 11 12
────────────────────────────────────
Mica (average particle size about 0.05mm) ○ − − − − − −
(Average particle diameter of about 0.1 mm)-○-----
(Average particle diameter of about 0.5 mm) − − ○ − − − −
(Average particle diameter of about 1.0 mm) − − − ○ − − −
(Average particle diameter of about 1.5 mm) − − − − ○ − −
(Average particle diameter of about 2.0 mm) − − − − − ○ −
(Average particle size of about 3.0 mm) − − − − − − ○
────────────────────────────────────
Evaluation item Glitter △ ○ ◎ ◎ ◎ ◎ ◎
Flip flop ○ ○ ◎ ◎ ◎ ◎ ◎
────────────────────────────────────
上記表２より、雲母の平均粒径は意匠性を考慮するならば０．１ｍｍ以上が好ましく、特に０．５ｍｍ以上で優れた輝きを得ることができる。一方、２．０ｍｍを越えるとザラザラした感触が生じ、各種用途への適用も悪くなる傾向にある。従って、２．０ｍｍ以下、特に好ましくは１．５ｍｍ以下であることが好ましい。 From Table 2 above, the average particle size of mica is preferably 0.1 mm or more if design properties are taken into consideration, and particularly excellent brightness can be obtained at 0.5 mm or more. On the other hand, when it exceeds 2.0 mm, a rough feel is produced, and application to various uses tends to be poor. Accordingly, it is preferably 2.0 mm or less, particularly preferably 1.5 mm or less.
実施例２〜５
実施例１と同じ大粒径薄片状天然雲母を用いて、硫酸チタニルの添加量を変えた以外は同じ工程で各種複合材料を得た。
────────────────────────────────────――――
実施例 大粒径 硫酸チタニル量 生成量 ＴｉＯ２ 色調 二酸化チタン
薄片状雲母 被覆量
────────────────────────────────────――――
２ １００ｇ １３８ｍｌ １２０ｇ アナターゼ ギラギラと １８重量％
輝いた
黄色干渉色
３ １００ｇ １５６ｍｌ １２３ｇ アナターゼ ギラギラと ２０重量％
輝いた
赤色干渉色
４ １００ｇ ２３１ｍｌ １３５ｇ アナターゼ ギラギラと ２７重量％
輝いた
青色色干渉色
５ １００ｇ ２９４ｍｌ １４４ｇ アナターゼ ギラギラと ３２重量％
輝いた
緑色干渉色
────────────────────────────────────――――
Examples 2-5
Using the same large particle size flaky natural mica as in Example 1, various composite materials were obtained in the same process except that the addition amount of titanyl sulfate was changed.
──────────────────────────────────── ――――
Example Large particle size Amount of titanyl sulfate Amount produced TiO 2 color tone Titanium dioxide Flaky mica Cover amount ────────────────────────────── ────── ――――――
2 100g 138ml 120g Anatase Giragira and 18% by weight
Shined
Yellow interference color 3 100g 156ml 123g anatase glare and 20% by weight
Shined
Red interference color 4 100g 231ml 135g Anatase Gira Gira 27%
Shined
Blue interference color 5 100g 294ml 144g Anatase Giragira and 32wt%
Shined
Green interference color ──────────────────────────────────── ――――――
実施例６〜１０
大粒径薄片状合成雲母１００ｇをイオン交換水１Ｌに添加してプロペラにて十分攪拌し、均一に分散させた。得られた分散液に塩化スズ３．５ｇを含む希塩酸水溶液２０mlを加えこれに苛性ソーダ水溶液を加えてｐＨを１．８に調整した。ｐＨ調整済み分散液を攪拌しながら加熱して８０℃の温度とした。この状態を保ちながら１時間攪拌した。さらにこの加熱攪拌分散液にｐＨを１．８に保持しながら苛性ソーダ水溶液と２モル濃度の四塩化チタン水溶液とを加えた。四塩化チタン水溶液添加後２時間加熱熟成させた。放冷後、濾過水洗し１２０℃で乾燥した。乾燥後９００℃にて２時間焼成した。得られた大粒径薄片状合成雲母複合材料は実施例１と同様にＸ線回折と走査型電子顕微鏡で解析した。
Examples 6-10
100 g of flaky synthetic mica having a large particle size was added to 1 L of ion-exchanged water and sufficiently stirred with a propeller to be uniformly dispersed. To the obtained dispersion was added 20 ml of a dilute hydrochloric acid solution containing 3.5 g of tin chloride, and an aqueous sodium hydroxide solution was added thereto to adjust the pH to 1.8. The pH adjusted dispersion was heated to 80 ° C. with stirring. While maintaining this state, the mixture was stirred for 1 hour. Further, a caustic soda aqueous solution and a 2 molar titanium tetrachloride aqueous solution were added to the heated stirring dispersion while maintaining the pH at 1.8. After the addition of the aqueous titanium tetrachloride solution, the mixture was aged by heating for 2 hours. After standing to cool, it was washed with filtered water and dried at 120 ° C. After drying, it was calcined at 900 ° C. for 2 hours. The obtained large particle size flaky synthetic mica composite material was analyzed by X-ray diffraction and a scanning electron microscope in the same manner as in Example 1.
────────────────────────────────────――――
実施例 大粒径 硫酸チタニル量 生成量 ＴｉＯ２ 色調 二酸化チタン
薄片状雲母 被覆量
────────────────────────────────────――――
６ １００ｇ １０５ｍｌ １１４ｇ ルチル ギラギラと １４重量％
輝いた銀色
７ １００ｇ １４０ｍｌ １２０ｇ ルチル ギラギラと １８重量％
輝いた
黄色干渉色
８ １００ｇ １６０ｍｌ １２３ｇ ルチル ギラギラと ２０重量％
輝いた
赤色干渉色
９ １００ｇ ２３０ｍｌ １３５ｇ ルチル ギラギラと ２７重量％
輝いた
青色干渉色
１０ １００ｇ ２９５ｍｌ １４５ｇ ルチル ギラギラと ３２重量％
輝いた
緑色干渉色
────────────────────────────────────――――
──────────────────────────────────── ――――
Example Large particle size Amount of titanyl sulfate Amount produced TiO 2 color tone Titanium dioxide Flaky mica Cover amount ────────────────────────────── ────── ――――――
6 100g 105ml 114g Rutile and 14% by weight
Shiny silver color 7 100g 140ml 120g Rutile Giragira and 18% by weight
Shined
Yellow interference color 8 100g 160ml 123g Rutile Giragira and 20% by weight
Shined
Red interference color 9 100g 230ml 135g Rutile Giragira and 27% by weight
Shined
Blue interference color 10 100g 295ml 145g Rutile Giragira and 32% by weight
Shined
Green interference color ──────────────────────────────────── ――――――
実施例１１
大粒径薄片状合成雲母１００ｇをイオン交換水１Ｌに添加してプロペラにて十分に攪拌し均一に分散させた。得られた分散液に濃度４０重量％の硫酸チタニル水溶液６２５ｍｌを加えて攪拌しながら加熱し６時間沸騰させた。放冷後、濾過水洗し、１００℃で乾燥させた。乾燥後５００℃で６時間焼成した。放冷して、ギラギラと輝いた彩度の高い緑色の干渉色の二酸化チタンで被覆された雲母系複合材料１９５ｇを得た。Ｘ線回析結果、二酸化チタンはアナターゼであり、走査型電子顕微鏡で観察すると粒子表面が均一に被覆されていた。また、蛍光Ｘ線分析で二酸化チタンを定量した結果５０重量％であった。
Example 11
100 g of flaky synthetic mica having a large particle size was added to 1 L of ion-exchanged water and sufficiently stirred with a propeller to uniformly disperse. To the obtained dispersion, 625 ml of an aqueous titanyl sulfate solution having a concentration of 40% by weight was added and heated with stirring to boil for 6 hours. After standing to cool, it was washed with filtered water and dried at 100 ° C. After drying, it was calcined at 500 ° C. for 6 hours. The mixture was allowed to cool to obtain 195 g of a mica-based composite material coated with titanium dioxide having a high-saturation green interference color that was glittering. As a result of X-ray diffraction, titanium dioxide was anatase, and the particle surface was uniformly coated when observed with a scanning electron microscope. Further, the result of quantitative determination of titanium dioxide by fluorescent X-ray analysis was 50% by weight.
実施例１２
大粒径薄片状合成雲母１００ｇをイオン交換水５００ｍｌに添加してプロペラにて十分に攪拌し均一に分散させた。得られた分散液に、塩化第二鉄０．１ｇと尿素０．２ｇとを加えて十分に攪拌し溶解させた。溶解後攪拌しながら加熱し、８０℃以上の温度で４時間熟成した。放冷後、濾過水洗し、１００℃で乾燥させた。乾燥後２００℃で２時間低温焼成し、淡橙色の外観をもった酸化鉄で被覆された雲母系複合材料９８ｇを得た。Ｘ線回析の結果では回析線に変化はみられないが蛍光Ｘ線分析の結果、鉄を０．１重量％含有していることが定量された。しかも走査型電子顕微鏡観察の結果、大粒径薄片状粒子の表面に被覆されていることが分かった。
Example 12
100 g of flaky synthetic mica having a large particle size was added to 500 ml of ion-exchanged water and sufficiently stirred with a propeller to uniformly disperse. To the obtained dispersion, 0.1 g of ferric chloride and 0.2 g of urea were added and sufficiently stirred to dissolve. After dissolution, the mixture was heated with stirring and aged at a temperature of 80 ° C. or higher for 4 hours. After standing to cool, it was washed with filtered water and dried at 100 ° C. After drying, it was calcined at 200 ° C. for 2 hours, and 98 g of a mica-based composite material coated with iron oxide having a pale orange appearance was obtained. As a result of X-ray diffraction, no change was observed in the diffraction line, but as a result of fluorescent X-ray analysis, it was quantified to contain 0.1% by weight of iron. Moreover, as a result of observation with a scanning electron microscope, it was found that the surface of the large-sized flaky particles was coated.
実施例１３
実施例７で得た、二酸化チタン被覆大粒径薄片状合成雲母複合材料４０ｇを７００ｍｌのイオン交換水に添加してプロペラにて十分攪拌し、均一に分散させた。得られた分散液に修酸第２鉄アンモニウム４．５ｇと尿素１．０ｇ秤り、これにイオン交換水１００ｍｌを加えて、溶解するまでプロペラ攪拌した。この水溶液を二酸化チタン被覆大粒径薄片状合成雲母複合材料が均一分散している分散液に加え、攪拌しながら８０℃に加熱し、４時間加熱攪拌を続けた。４時間終了後、分散液を放冷し、濾過水洗し、１００℃で７時間乾燥した。乾燥後、放冷し、彩度が高く橙色でギラギラと輝いた黄色の干渉色をもった複合材料４１ｇを得た。更にこのものを９００℃で４時間焼成した。放冷後、鮮やかで彩度の高い黄色でギラギラと輝いた黄色の干渉色をもった複合材料４０ｇを得た。得られた複合材料のＸ線回析から合成雲母と二酸化チタンのルチル及び鉄と二酸化チタンの化合物である擬板チタン鉄鉱（Ｆｅ２ＴｉＯ５）が確認された。また、走査型電子顕微鏡観察によれば、粒子表面に若干粒子の大きい粒状（約０．０８μｍ）の粒子が点在しており、その下に０．０２μｍの超微粒子の粒状粒子が粒子表面全体を均一に被覆していた。このことより本実施例にかかる複合材料は、二酸化チタンと擬板チタン鉄鉱で被覆された大粒径薄片状合成雲母複合材料で、鉄の量は蛍光Ｘ線分析の結果０．７重量％であった。
Example 13
40 g of the titanium dioxide-coated large particle size flaky synthetic mica composite material obtained in Example 7 was added to 700 ml of ion-exchanged water and sufficiently stirred with a propeller to uniformly disperse. To the obtained dispersion, 4.5 g of ferric ammonium oxalate and 1.0 g of urea were weighed, and 100 ml of ion-exchanged water was added thereto and stirred with a propeller until dissolved. This aqueous solution was added to a dispersion in which the titanium dioxide-coated large particle size flaky synthetic mica composite material was uniformly dispersed, heated to 80 ° C. with stirring, and heated and stirred for 4 hours. After 4 hours, the dispersion was allowed to cool, washed with filtered water, and dried at 100 ° C. for 7 hours. After drying, the mixture was allowed to cool to obtain 41 g of a composite material having a high chroma and a yellow interference color that was orange and brilliant. Further, this was baked at 900 ° C. for 4 hours. After allowing to cool, 40 g of a composite material having a bright, highly saturated yellow, glittering yellow interference color was obtained. From the X-ray diffraction of the obtained composite material, synthetic mica, rutile titanium dioxide, and pseudo-plate titanite (Fe 2 TiO 5 ), which is a compound of iron and titanium dioxide, were confirmed. Further, according to observation with a scanning electron microscope, granular particles (approximately 0.08 μm) having slightly larger particles are scattered on the particle surface, and 0.02 μm ultrafine particle particles are scattered under the entire particle surface. Was uniformly coated. From this, the composite material according to this example is a large particle size flaky synthetic mica composite material coated with titanium dioxide and pseudo-plate titanite, and the amount of iron is 0.7% by weight as a result of fluorescent X-ray analysis. there were.
実施例１４
実施例４で得た二酸化チタン被覆大粒径薄片状天然雲母複合材料４０ｇにイオン交換水７００ｍｌを加えてプロペラにて十分攪拌し、均一に分散させた。この分散液に塩化コバルトの６水塩１６ｇをイオン交換水１５０ｍｌに溶解させた液を加えた。次いで分散液を５０℃に加熱してから攪拌しながら１モル濃度の苛性ソーダー水溶液を毎分１００ｍｌの滴下速度で加えてｐＨが９．０になってから苛性ソーダの滴下を止め、２時間熟成させた。熟成終了後放冷し、濾過水洗して１００℃で５時間乾燥した。乾燥粉末を９００℃で４時間焼成した。放冷した複合材料は外観色が緑色を呈し、ギラギラと輝いた干渉色が赤味の青色を呈した光輝性の強い複合材料を４３ｇ得た。この材料のＸ線回析結果から、雲母と二酸化チタン及び二酸化チタンと酸化コバルトから生成されたチタン酸コバルトが確認された。また、走査型電子顕微鏡の観察から、大粒径薄片状粒子表面に０．５μｍの粒状粒子が点在しており、その下には０．０２μｍの超微粒子が観察された。更に蛍光Ｘ線分析からコバルトが４重量％被覆していることが確認された。そして、この複合材料を両面粘着テープに均一に塗布し、白と黒からなる隠蔽率試験紙に貼り、測色角度と変えて測色した。その結果、４５゜入射に対して０゜方向で測色すると緑色が強く反射され、正反射方向に近い３０゜で測色すると赤みの青色反射が強くみられた。すなわちコバルトとチタンの金属酸化物とを被覆し焼成した大粒径薄片状天然雲母複合材料は、外観色が緑色でギラギラと輝いた光輝性が強く、しかも、二色性を示すフリップ・フロップ効果を発現した。意匠性に優れた雲母系複合材料であった。
Example 14
To 40 g of the titanium dioxide-coated large particle size flaky natural mica composite material obtained in Example 4, 700 ml of ion exchange water was added and sufficiently stirred with a propeller to uniformly disperse. A solution prepared by dissolving 16 g of cobalt chloride hexahydrate in 150 ml of ion-exchanged water was added to this dispersion. Next, the dispersion is heated to 50 ° C., and a 1 molar aqueous caustic soda solution is added at a dropping rate of 100 ml per minute while stirring to stop the dripping of caustic soda from aging for 2 hours. It was. After aging, the mixture was allowed to cool, washed with filtered water, and dried at 100 ° C. for 5 hours. The dried powder was fired at 900 ° C. for 4 hours. The composite material that had been allowed to cool was obtained with 43 g of a highly brilliant composite material having a green appearance color and a brilliant interference color of reddish blue. From the result of X-ray diffraction of this material, mica and titanium dioxide and cobalt titanate produced from titanium dioxide and cobalt oxide were confirmed. Further, from observation with a scanning electron microscope, 0.5 μm granular particles were scattered on the surface of large flaky particles, and 0.02 μm ultrafine particles were observed below the particles. Furthermore, it was confirmed from the fluorescent X-ray analysis that 4% by weight of cobalt was coated. And this composite material was uniformly apply | coated to the double-sided adhesive tape, and it affixed on the concealment rate test paper which consists of white and black, and changed the colorimetric angle, and measured the color. As a result, when the color was measured in the 0 ° direction with respect to 45 ° incidence, green was strongly reflected, and when the color was measured at 30 ° close to the regular reflection direction, reddish blue reflection was strongly observed. In other words, the large particle size flaky natural mica composite material coated with cobalt and titanium metal oxide and fired is a flip-flop effect that exhibits a brilliant, brilliant, brilliant appearance with a green appearance color. Expressed. It was a mica-based composite material with excellent design.
実施例１５
実施例１４と同じ工程で二酸化チタン被覆大粒径薄片状天然雲母複合材料にコバルト化合物を被覆した複合材料２０ｇに、炭酸リチウム２．５ｇを混合し９５０℃で８時間焼成した。放冷後、高彩度の青緑色の外観を呈したギラギラと輝いた材料２２ｇを得た。この材料のＸ線回析結果から、雲母と二酸化チタン及び二酸化チタンと酸化コバルトと酸化リチウムとから生成されたチタン酸リチウムコバルトからなることが確定された。また、走査型電子顕微鏡の観察から大粒径薄片状粒子表面に１μｍの粒状粒子が点在しており、その下には０．０２μｍの超微粒子が均一に全面を被覆していた。更に蛍光Ｘ線分析からリチウムが２．５重量％被覆されていることが確認された。そしてこの複合材料を両面粘着テープに均一に塗布し、白と黒からなる隠蔽率試験紙に貼り、測色角度を変えて測色した。その結果、４５゜入射に対して０゜方向で測色すると青緑色が強く反射され、正反射方向に近い３０゜で測色すると赤みの青色反射が強くみられた。すなわちチタンとコバルト及びリチウムの金属酸化物を被覆し、焼成した大粒径薄片状天然雲母複合材料は、外観色が彩度の高い青緑色でギラギラと輝いた光輝性が強く、しかも青緑色と赤みの青色干渉色とを呈する、二色性を示すフリップ・フロップ効果を発現した。本実施例にかかる材料は、意匠性に優れた雲母系複合材料であった。
Example 15
In the same process as in Example 14, 2.5 g of lithium carbonate was mixed with 20 g of a composite material obtained by coating a titanium dioxide-coated large particle size flaky natural mica composite material with a cobalt compound, and calcined at 950 ° C. for 8 hours. After standing to cool, 22 g of a brilliant and bright material having a blue-green appearance with high saturation was obtained. From the X-ray diffraction results of this material, it was determined that it consists of mica and titanium dioxide and lithium cobalt titanate produced from titanium dioxide, cobalt oxide and lithium oxide. Also, from observation with a scanning electron microscope, 1 μm granular particles were scattered on the surface of the large flaky particles, and 0.02 μm ultrafine particles uniformly covered the entire surface under the particles. Furthermore, it was confirmed from the fluorescent X-ray analysis that 2.5% by weight of lithium was coated. Then, this composite material was uniformly applied to a double-sided adhesive tape and affixed to a white and black concealment rate test paper, and colorimetry was performed by changing the colorimetric angle. As a result, when the color was measured in the 0 ° direction with respect to 45 ° incidence, blue-green was strongly reflected, and when the color was measured at 30 ° close to the regular reflection direction, reddish blue reflection was strongly observed. In other words, the large particle size flaky natural mica composite material coated with a metal oxide of titanium, cobalt, and lithium and calcined with a bright blue-green color with a high appearance color and a brilliant glitter, A flip-flop effect exhibiting dichroism exhibiting a reddish blue interference color was developed. The material according to this example was a mica-based composite material having excellent design properties.
実施例１６
実施例１０で得た二酸化チタン被覆大粒径薄片状合成雲母複合材料４０ｇを７００ｍｌのイオン交換水に添加してプロペラにて十分攪拌し均一に分散させた。得られた分散液に硫酸ニッケル１０ｇと尿素１ｇとを１００ｍｌのイオン交換水に溶解させ水溶液を加えた。攪拌しながら沸騰させ４時間熟成した。熟成後放冷し、濾過水洗して１００℃で乾燥した。得られた材料は、外観色が灰色のギラギラしたものであり４２ｇ得られた。得られた材料２０ｇに炭酸ナトリム３ｇを混合して、１２００℃で２時間焼成した。放冷後、彩度の高い黄色の外観色を持った、ギラギラと輝きの強い青緑色の干渉色をもった材料２１ｇを得た。得られた材料のＸ線回析結果から、合成雲母と二酸化チタン及びナトリウムとニッケルとチタネートの化合物であるナトリウムニッケルテタネットがわずかではあるが確認された。また、走査型電子顕微鏡から大粒径薄片状粒子の表面が溶融している状態が観察された。更に蛍光Ｘ線分析の結果、ナトリウムが５．５重量％でリチウムが７重量％であった。すなわち本品は合成雲母が二酸化チタンとナトリウムニッケルチタネートで被覆された大粒径薄片状合成雲母複合材料で彩度の高い黄色の外観色をもち、ギラギラと輝きの強い青緑色の干渉色をもち、黄色と干渉色との二色性をもった意匠性の高い雲母系複合材料であった。
Example 16
40 g of the titanium dioxide-coated large particle size flaky synthetic mica composite material obtained in Example 10 was added to 700 ml of ion-exchanged water and sufficiently stirred with a propeller to uniformly disperse. To the obtained dispersion, 10 g of nickel sulfate and 1 g of urea were dissolved in 100 ml of ion exchange water, and an aqueous solution was added. The mixture was boiled with stirring and aged for 4 hours. After aging, it was allowed to cool, washed with filtered water and dried at 100 ° C. The obtained material was glaring with a gray appearance color, and 42 g was obtained. 20 g of the obtained material was mixed with 3 g of sodium carbonate and baked at 1200 ° C. for 2 hours. After standing to cool, 21 g of a material having a high-saturation yellow appearance color and having a brilliant and bright blue-green interference color was obtained. From the result of X-ray diffraction of the obtained material, it was confirmed that there was a slight amount of synthetic mica and titanium dioxide and sodium nickel tetanet which is a compound of sodium, nickel and titanate. In addition, a state where the surface of the large particle flaky particles was melted was observed from a scanning electron microscope. Furthermore, as a result of fluorescent X-ray analysis, sodium was 5.5% by weight and lithium was 7% by weight. That is, this product is a large particle size flaky synthetic mica composite material in which synthetic mica is coated with titanium dioxide and sodium nickel titanate, and has a yellow appearance color with high saturation, and has a bright blue-green interference color with glitter. It was a highly mica-based composite material having a dichroic property of yellow and interference color.
実施例１７
実施例１で得た、二酸化チタン被覆大粒径薄片状天然雲母４０ｇを７００ｍｌのイオン交換水に添加してプロペラにて十分攪拌し均一に分散させた。得られた分散液に、オキシ塩化ジルコニウム２．１ｇをイオン交換水５０ｍｌに溶解させたものを加えて、攪拌しながら加熱して沸騰させ３時間熟成した。熟成後放冷して濾過水洗した。水洗後得られた材料を６００ｍｌのイオン交換水に添加してプロペラにて十分攪拌し均一に分散させた。得られた分散液に、硫酸アルミニウム２８ｇと尿素２．３ｇとをイオン交換水１００ｍｌに溶解させたものを加えた。攪拌しながら加熱した。８０℃で４時間熟成した。熟成後、放冷して濾過水洗し１００℃で乾燥した。得た材料を２００℃で１６時間焼成した。放冷後、白色のギラギラと輝いた材料４２ｇを得た。得られた材料５ｇを５０容量％のエタノール水容液５０ｍｌに加えてプロペラにて攪拌し均一に分散させた。また、比較として実施例１で得られた材料を上記と同様な方法でエタノールに分散させた。各々の分散液に２．５ＫｗのＸｅランプで３０時間照射した。その結果、オキシ塩化ジルコニウムと硫酸アルミニウムで処理した材料はギラギラと輝いていたが、比較として実施例１で得た材料は灰黒色の外観色をもちギラギラと輝いた材料に変わっていた。すなわち処理した材料はより一層耐光性に強いものであった。
Example 17
40 g of the titanium dioxide-coated large particle size flaky natural mica obtained in Example 1 was added to 700 ml of ion-exchanged water and sufficiently stirred with a propeller to uniformly disperse. A solution obtained by dissolving 2.1 g of zirconium oxychloride in 50 ml of ion-exchanged water was added to the obtained dispersion, and the mixture was heated to boiling while stirring and aged for 3 hours. After aging, it was allowed to cool and washed with filtered water. The material obtained after washing with water was added to 600 ml of ion-exchanged water and sufficiently stirred with a propeller to uniformly disperse. A solution obtained by dissolving 28 g of aluminum sulfate and 2.3 g of urea in 100 ml of ion-exchanged water was added to the obtained dispersion. Heated with stirring. Aging was performed at 80 ° C. for 4 hours. After aging, the mixture was allowed to cool, washed with filtered water, and dried at 100 ° C. The resulting material was fired at 200 ° C. for 16 hours. After standing to cool, 42 g of white glittering material was obtained. 5 g of the obtained material was added to 50 ml of a 50% by volume ethanol aqueous solution and stirred with a propeller to uniformly disperse. For comparison, the material obtained in Example 1 was dispersed in ethanol in the same manner as described above. Each dispersion was irradiated with a 2.5 Kw Xe lamp for 30 hours. As a result, the material treated with zirconium oxychloride and aluminum sulfate was brilliant, but for comparison, the material obtained in Example 1 had a gray-black appearance color and changed to a brilliant material. That is, the processed material was much more resistant to light.
得られた複合材料のＸ線回析からは雲母と二酸化チタンのアナターゼ型のみが確認された。走査型電子顕微鏡によると大粒子表面に粒子径が０．５μｍの針状径粒子と０．１μｍ以下の粒状が点在していた。更にＥＤＸ（エネルギー分散型Ｘ線分析）にて点分析を行った結果、針状粒子はアルミニウムの化合物、粒状粒子はジルコニウムの化合物からなっていた。すなわち、大粒径薄片状雲母複合材料はアルミニウムとジルコニム化合物と二酸化チタンで被覆された。耐光性の強いギラギラと輝いた材料であった。しかも、アルミニウムは定量の結果、１重量％であり、ジルコニウムは定量の結果０．８重量％であった。 From the X-ray diffraction of the obtained composite material, only an anatase type of mica and titanium dioxide was confirmed. According to the scanning electron microscope, needle-like particles having a particle diameter of 0.5 μm and particles having a particle diameter of 0.1 μm or less were scattered on the surface of the large particles. Furthermore, as a result of performing point analysis by EDX (energy dispersive X-ray analysis), the acicular particles were composed of an aluminum compound and the granular particles were composed of a zirconium compound. That is, the large particle size flaky mica composite material was coated with aluminum, a zirconium compound, and titanium dioxide. It was a glittering material with strong light resistance. Moreover, aluminum was 1% by weight as a result of quantification, and zirconium was 0.8% by weight as a result of quantification.
実施例１８
実施例７で得た二酸化チタン被覆大粒径薄片状合成雲母複合材料４０ｇを７００ｍｌのイオン交換水に添加してプロペラにて十分攪拌し均一に分散させた。得られた分散液に塩化亜鉛８ｇと尿素１８ｇとを０．１Ｎ塩酸水溶液１００ｍｌに加え溶解させ、これを加えた。攪拌しながら加熱し、８０℃にて４時間熟成させた。熟成後放冷し濾過水洗した。このスラリーにイオン交換水６００ｍｌを加えてプロペラにて均一に攪拌した。均一分散液に苛性ソーダー水溶液を加えｐＨを９に調整し、８０℃に加熱した。この加熱攪拌分散液に、水ガラス２ｇを含む水溶液５０ｍｌと１．０Ｎ塩酸水溶液とを同時に滴下した。但しｐＨ９を保つと共に水ガラスの滴下速度は毎分１０ｍｌの速度で加え、添加終了後２時間熟成した。熟成後濾過・水洗し１００℃で乾燥した。乾燥材料は白色のギラギラ輝いた黄色の干渉色をもったもので、４３ｇ得られた。得られた材料はＸ線回析から合成雲母と二酸化チタンのルチル及び酸化亜鉛が認められた。また、走査型電子顕微鏡観察から大粒子表面が０．５μｍの針状の粒子と０．０２μｍの粒状の粒子が観察できた。更にＥＤＸでの点分析から針状は亜鉛化合物であり、０．０２μｍはチタン化合物であった。走査型電子顕微鏡での観察倍率を１０万倍にすると針状粒子が更に細かい０．０１μｍ以下の粒子で被覆されており、これがケイ素化合物であった。このことから、この材料は大粒径薄片状合成雲母が二酸化チタンと酸化亜鉛及びケイ素化合物で被覆された複合雲母材料であることが解った。更にまた、化学分析した結果、酸化亜鉛は１０重量％で、ケイ素は０．８重量％であった。
Example 18
40 g of the titanium dioxide-coated large particle size flaky synthetic mica composite material obtained in Example 7 was added to 700 ml of ion-exchanged water and sufficiently stirred with a propeller to uniformly disperse. To the obtained dispersion liquid, 8 g of zinc chloride and 18 g of urea were added and dissolved in 100 ml of 0.1N hydrochloric acid aqueous solution, and this was added. The mixture was heated with stirring and aged at 80 ° C. for 4 hours. After aging, it was allowed to cool and washed with filtered water. To this slurry, 600 ml of ion-exchanged water was added and stirred uniformly with a propeller. A caustic soda aqueous solution was added to the uniform dispersion to adjust the pH to 9 and heated to 80 ° C. To this heated stirring dispersion, 50 ml of an aqueous solution containing 2 g of water glass and 1.0N aqueous hydrochloric acid were simultaneously added dropwise. However, pH 9 was maintained and the dropping rate of water glass was added at a rate of 10 ml per minute, and the mixture was aged for 2 hours after the addition was completed. After aging, it was filtered, washed with water and dried at 100 ° C. The dried material had a white, glittery, yellow interference color, yielding 43 g. From the X-ray diffraction of the obtained material, synthetic mica, rutile titanium dioxide and zinc oxide were observed. Further, from observation with a scanning electron microscope, needle-like particles having a large particle surface of 0.5 μm and granular particles of 0.02 μm were observed. Further, from the point analysis by EDX, the needle shape was a zinc compound, and 0.02 μm was a titanium compound. When the observation magnification with a scanning electron microscope was increased to 100,000, the acicular particles were coated with finer particles of 0.01 μm or less, which were silicon compounds. This indicates that this material is a composite mica material in which large particle size flaky synthetic mica is coated with titanium dioxide, zinc oxide, and a silicon compound. Furthermore, as a result of chemical analysis, zinc oxide was 10% by weight and silicon was 0.8% by weight.
実施例１９
実施例６で得た二酸化チタン被覆大粒径薄片状合成雲母複合材料４０ｇを７００ｍｌのイオン交換水に添加してプロペラにて十分攪拌し均一に分散させた。得られた分散液に硝酸ビスマス６ｇと尿素２ｇとをイオン交換水１００ｍｌに溶解させたものを加えた。攪拌しながら加熱し、８０℃で４時間熟成させた。熟成後放冷し濾過水洗し、１００℃で８時間乾燥させた。乾燥後４００℃で２時間焼成した。放冷後、黄色のギラギラと輝いた材料４４ｇを得た。この材料のＸ線回析から合成雲母と二酸化チタンのルチル及び酸化ビスマスが確認された。また、走査型電子顕微鏡から大粒子表面が０．０３μｍの粒状粒子が点在し更にその下には若干小さい０．０２μｍ程度の粒状粒子が表面全面を被覆していた。そして、ＥＤＸによる点分析から点在粒子がビスマスであり、その下の粒子がチタンであることが解った。また、蛍光Ｘ線分析からビスマスは６重量％であった。このことから、この材料は、酸化ビスマスと二酸化チタンで被覆された大粒径薄片状合成雲母で、黄色の外観色をもちギラギラと輝いた複合材料である。
Example 19
40 g of the titanium dioxide-coated large particle size flaky synthetic mica composite material obtained in Example 6 was added to 700 ml of ion-exchanged water and sufficiently stirred with a propeller to uniformly disperse. A solution obtained by dissolving 6 g of bismuth nitrate and 2 g of urea in 100 ml of ion-exchanged water was added to the obtained dispersion. The mixture was heated with stirring and aged at 80 ° C. for 4 hours. After aging, it was allowed to cool, washed with filtered water, and dried at 100 ° C. for 8 hours. After drying, it was calcined at 400 ° C. for 2 hours. After standing to cool, 44 g of yellow glittering material was obtained. X-ray diffraction of this material confirmed synthetic mica, titanium dioxide rutile and bismuth oxide. Further, granular particles having a large particle surface of 0.03 μm were scattered from a scanning electron microscope, and further, a slightly smaller granular particle of about 0.02 μm covered the entire surface. And it was found from the point analysis by EDX that the interspersed particles are bismuth and the underlying particles are titanium. Further, bismuth was 6% by weight from fluorescent X-ray analysis. From this, this material is a composite material with a large particle size flaky synthetic mica coated with bismuth oxide and titanium dioxide, which has a yellow appearance color and shines brightly.
実施例２０
実施例１０で得た二酸化チタン被覆大粒径薄片状合成雲母複合材料４０ｇを７００ｍｌのイオン交換水に添加してプロペラにて十分攪拌して均一に分散させた。得られた分散液に、オキシ塩化タングステン５ｇをイオン交換水１００ｍｌに溶解させた水溶液を加えた。分散液を攪拌しながら８０℃に加熱し、０．２Ｎの苛性カリ水溶液を毎分１０ｍｌの速度で滴下し、液のｐＨが９になるまで苛性カリ水溶液を滴下した。ｐＨ９の状態で４時間熟成した。熟成後放冷し濾過水洗し、１００℃で乾燥した。乾燥材料を５００℃で２時間焼成した。放冷後、淡黄色のギラギラと輝いた緑色の干渉色をもった材料４３ｇを得た。この材料のＸ線回析から合成雲母と二酸化チタンのルチル及び酸化タングステンが確認された。また、走査型電子顕微鏡観察から大粒子表面が０．３μｍの不定型粒子が点在しており、その下には０．０２μｍと小さい粒状粒子が全面を被覆していることが解った。そしてＥＤＸによる点分析から点在している粒子がタングステンであり、その下の粒子はチタンであった。また、蛍光Ｘ線分析からタングステンは５重量％であった。このことからこの材料は酸化タングステンと二酸化チタンで被覆された大粒径薄片状合成雲母で、淡黄色の外観色を呈するギラギラと輝き緑色の干渉色をもち、淡黄色と緑色干渉色との二色性をもった意匠性の高い雲母系複合材料であった
Example 20
40 g of the titanium dioxide-coated large particle size flaky synthetic mica composite material obtained in Example 10 was added to 700 ml of ion-exchanged water and sufficiently stirred with a propeller to uniformly disperse. To the obtained dispersion, an aqueous solution in which 5 g of tungsten oxychloride was dissolved in 100 ml of ion exchange water was added. The dispersion was heated to 80 ° C. with stirring, a 0.2N aqueous solution of caustic potash was added dropwise at a rate of 10 ml per minute, and the aqueous caustic potash solution was added dropwise until the pH of the liquid reached 9. The mixture was aged at pH 9 for 4 hours. After aging, it was allowed to cool, washed with filtered water, and dried at 100 ° C. The dried material was calcined at 500 ° C. for 2 hours. After standing to cool, 43 g of a material having a pale yellow glitter and a bright green interference color was obtained. X-ray diffraction of this material confirmed synthetic mica, titanium dioxide rutile and tungsten oxide. Further, from observation with a scanning electron microscope, it was found that irregular particles having a large particle surface of 0.3 μm were scattered, and below that, granular particles as small as 0.02 μm covered the entire surface. And the particle | grains scattered from the point analysis by EDX were tungsten, and the particle | grains under it were titanium. Moreover, tungsten was 5 weight% from the fluorescent X ray analysis. From this, this material is a large particle size flaky synthetic mica coated with tungsten oxide and titanium dioxide. It has a pale yellow appearance color and a bright green interference color. It was a highly mica-based composite material with color and design
Claims (8)
該雲母表面に形成された金属酸化物および／又は金属水酸化物の一種又は二種以上からなる被覆層と、からなり、
金属酸化物が二酸化チタンを含む場合は二酸化チタンはルチル型及び／又はアナターゼ型であることを特徴とする雲母系複合材料。 A large particle size flaky mica having a particle diameter of 0.1 mm or more and less than 0.5 mm and a particle thickness of 0.2 to 2 μm;
A coating layer made of one or more metal oxides and / or metal hydroxides formed on the mica surface;
When the metal oxide contains titanium dioxide, the mica-based composite material is characterized in that the titanium dioxide is rutile type and / or anatase type.
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| US9045643B2 (en) | 2006-04-21 | 2015-06-02 | Nippon Sheet Glass Company Limited | Bright pigment, method for producing the pigment, and waterborne resin composition containing the pigment |
| US9107834B2 (en) | 2007-04-18 | 2015-08-18 | Nippon Sheet Glass Company, Limited | Bright pigment and cosmetic composition using the same |
| CN110407217A (en) * | 2019-08-29 | 2019-11-05 | 淄博三锐陶瓷科技有限公司 | The method of the waste lithium cell positive electrode preparation high light inorganic material of nanometer |
| JP7214276B1 (en) | 2022-04-18 | 2023-01-30 | サンヨー化成株式会社 | Handle material for plastic molded products, patterned plastic molded products containing the same, and method for producing handle material for plastic molded products |
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| JP7214276B1 (en) | 2022-04-18 | 2023-01-30 | サンヨー化成株式会社 | Handle material for plastic molded products, patterned plastic molded products containing the same, and method for producing handle material for plastic molded products |
| WO2023203823A1 (en) * | 2022-04-18 | 2023-10-26 | サンヨー化成株式会社 | Pattern material for plastic molded article, patterned plastic molded article having said material compounded therein, and method for producing pattern material for plastic molded article |
| JP2023158267A (en) * | 2022-04-18 | 2023-10-30 | サンヨー化成株式会社 | Pattern material for plastic molding, patterned plastic molding blended with the same, and method for manufacturing pattern material for plastic molding |
| KR20230159630A (en) * | 2022-04-18 | 2023-11-21 | 산요 가세이 가부시키가이샤 | Pattern material for plastic molded products, patterned plastic molded products mixed with the same, and method of manufacturing pattern materials for plastic molded products |
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