JP2009184921A - Potassium octatitanate particle - Google Patents
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本発明は、プラスチック、摩擦材、塗料、潤滑材、耐熱材、断熱材、紙の添加剤等に使用されるチタン酸カリウムに関し、特に衛生面に関わる形状的特性を重視したチタン酸カリウム粒子に関する。 The present invention relates to potassium titanate used for plastics, friction materials, paints, lubricants, heat-resistant materials, heat-insulating materials, paper additives, and the like, and particularly relates to potassium titanate particles that emphasize shape characteristics related to hygiene. .
チタン酸カリウムは、元来、長さが数μｍ〜数十μｍ、径が１μｍ以下の形状を有し、その形状は一般的に繊維状、針状、ウィスカー等と呼ばれている。その繊維形状を生かし、プラスチック、塗料、摩擦材等の分野で主に補強材として実用化され、広く普及している。しかし、繊維状粉末は、嵩高く、流動性が悪く、扱いにくいという性質がある。さらに繊維状粉末は粉塵が発生しやすく作業環境上の問題もある。 Potassium titanate originally has a shape with a length of several μm to several tens of μm and a diameter of 1 μm or less, and the shape is generally called a fiber shape, a needle shape, a whisker or the like. Taking advantage of its fiber shape, it has been put to practical use as a reinforcing material mainly in the fields of plastics, paints, friction materials, etc., and is widely spread. However, fibrous powders are bulky, have poor fluidity, and are difficult to handle. Furthermore, the fibrous powder is liable to generate dust and has a problem in the working environment.
アスベストの発ガン性が問題になっているが、その原因は繊維状の形状に関係するとの見方もある。アスベストに限らず、繊維材料について、スタントン（Ｓｔａｎｔｏｎ）の仮説では、繊維の径が０．２５μｍ以下で長さが８μｍ以上の繊維が催腫瘍性が高いとしている。しかし、工業的に有用な繊維材料は作業環境での規準を設け利用されている。ＩＬＯ（世界労働機関）では直径が３μｍ以下、長さが５μｍ以上かつ長さと直径との比が３以上の繊維を吸入性繊維としている。ＡＩＡ（国際石綿協会）、ＤＦＧ（Ｄｅｕｔｓｃｈｅ Ｆｏｒｓｃｈｕｎｇｓｇｅｍｅｉｎｓｃｈａｆｔ：ドイツ調査協会）も同様の繊維を繊維状ダストとして管理するものとしている。 The carcinogenicity of asbestos has become a problem, but there is a view that the cause is related to the fibrous shape. Not only asbestos, but also fiber materials, Stanton's hypothesis states that fibers having a fiber diameter of 0.25 μm or less and a length of 8 μm or more are highly tumorigenic. However, industrially useful fiber materials are used with standards in the working environment. In the ILO (World Labor Organization), fibers having a diameter of 3 μm or less, a length of 5 μm or more, and a length to diameter ratio of 3 or more are used as inhalable fibers. AIA (International Asbestos Association) and DFG (Deutsche Forschungsgeinschaft) also manage similar fibers as fibrous dust.
本発明は安全性の観点に立脚して、形状特性の優れた、吸入性繊維の形状、寸法を有しない、チタン酸カリウム粒子を提供することを目的とする。 An object of the present invention is to provide potassium titanate particles having excellent shape characteristics and not having the shape and dimensions of respirable fibers based on the viewpoint of safety.
本発明者はこの点に立脚して特願平１１−１０３０３３号を出願しているが、本発明はさらに安全性の高いチタン酸カリウムに関するものである。 The present inventor has applied for Japanese Patent Application No. 11-103033 based on this point, but the present invention relates to potassium titanate having higher safety.
本発明は、上記目的を達成するために鋭意開発されたもので、粒子の長径が２μｍ未満であることを特徴とするチタン酸カリウム粒子を提供する。より好ましくは１μｍ未満である粒子からなるものである。また、このチタン酸カリウムは、長径／短径比が５未満であることを特徴とする。 The present invention has been developed in order to achieve the above object, and provides potassium titanate particles characterized in that the major axis of the particles is less than 2 μm. More preferably, it consists of particles that are less than 1 μm. The potassium titanate has a major axis / minor axis ratio of less than 5.
さらに、本発明のチタン酸カリウム粒子の長径／短径比が２未満の粒子が９０％以上、３未満の粒子が９７％以上の個数割合であるものを提供する。 Furthermore, the present invention provides the potassium titanate particles according to the present invention in which the ratio of the major axis / minor axis ratio is less than 2 and the number ratio is less than 90% and less than 3%.
本発明のチタン酸カリウムはＫ2Ｏ・ｎＴｉＯ2（ｎ＝１〜１２）のものである。上記長径が２μｍ未満の特性を有する本発明に係るチタン酸カリウム粒子は、焼成によりＫ2Ｏを生成するＫ源として炭酸塩、水酸化物、硝酸塩、硫酸塩等の１種以上とＴｉＯ2や水酸化チタン等の１種以上のＴｉ源の混合物を焼成し、長径が２μｍ未満の粒子を生成させ、水を加えてスラリー化し、酸を加えて余分のＫを溶出して目的組成に変換し、脱水後、熱処理を経て製造することができる。 The potassium titanate of the present invention is K 2 O · nTiO 2 (n = 1 to 12). The potassium titanate particles according to the present invention having the characteristic that the major axis is less than 2 μm are one or more of carbonate, hydroxide, nitrate, sulfate and the like as a K source for producing K 2 O by firing, TiO 2 and A mixture of one or more Ti sources such as titanium hydroxide is baked to produce particles having a major axis of less than 2 μm, added water to form a slurry, and acid is added to elute excess K to convert it to the target composition. It can be manufactured through heat treatment after dehydration.
また、Ｋ源とＴｉ源にＫ以外のアルカリ金属（Ｌｉ，Ｎａ，Ｒｂ，Ｃｓ）の炭酸塩、水酸化物、硝酸塩、硫酸塩、ハロゲン化アルカリ等の１種以上を少量添加配合した混合物を焼成し、長径が２μｍ未満の粒子を生成させることもできる。Ｋ以外のアルカリ金属の添加は、焼成時の融点を低下させることで、より低温での合成反応が完結し、繊維状への結晶成長が抑制されるものと思われる。 In addition, a mixture in which a small amount of one or more of carbonates, hydroxides, nitrates, sulfates, alkali halides, etc. of alkali metals (Li, Na, Rb, Cs) other than K is added to the K source and Ti source. It is possible to generate particles having a major axis of less than 2 μm by firing. The addition of an alkali metal other than K is considered to lower the melting point during firing, thereby completing the synthesis reaction at a lower temperature and suppressing the crystal growth into a fibrous form.
なお、アルカリ金属は、本発明のチタン酸カリウムの結晶構造に若干固溶するが、目的のＸ線回折図を満足する範囲内で使用される。 The alkali metal is slightly dissolved in the crystal structure of potassium titanate of the present invention, but is used within the range satisfying the target X-ray diffraction pattern.
このようにして得られた長径が短かく、長径／短径比の小さいチタン酸カリウム粒子はＸ線回折において、回折強度が弱く、半価幅の拡い回折線を示す。このことは結晶性が乏しいことを示しており、繊維状でないことを示している。また、合成条件によっては、粒子が厚さの薄い扁平な形状の粒子が得られる。この扁平な粒子をＸ線回折するとその回折図の特徴の１つに、（ｈｋｌ）で示されるミラー指数の（ｈ００）面／（０ｋ０）面の回折強度が３以下であることが認められる。これは、（０ｋ０）の結晶面が配向していることに起因しているものと思われる。従来の繊維状のチタン酸カリウムが、ｂ軸方向に伸長しているのに対し、本発明のチタン酸カリウムは厚さが薄く扁平な粒子が観察されることからもａ軸、ｃ軸の２方向への成長が大きいものと考えられる。このようなチタン酸カリウム粒子もまた繊維性がなく安全上好適なものである。 The thus obtained potassium titanate particles having a short major axis and a small major axis / minor axis ratio show a diffraction line having a weak diffraction intensity and a wide half-value width in X-ray diffraction. This indicates that the crystallinity is poor and it is not fibrous. In addition, depending on the synthesis conditions, particles having a flat shape with thin particles can be obtained. When this flat particle is X-ray diffracted, one of the features of the diffraction diagram shows that the diffraction intensity of the (h00) plane / (0k0) plane of the Miller index indicated by (hkl) is 3 or less. This seems to be due to the fact that the (0k0) crystal plane is oriented. The conventional fibrous potassium titanate extends in the b-axis direction, whereas the potassium titanate of the present invention has thin and flat particles. Growth in the direction is considered to be large. Such potassium titanate particles also have no fiber property and are suitable for safety.
なお、本発明のチタン酸カリウム粒子には用途上問題のない範囲のものにはＫ源との未反応のＴｉＯ2やチタン酸カリウムの熱分解で生成したＴｉＯ2が少量共存していてもよい。さらに、１次粒子が集合した２次粒子を含んでいてもよい。 Note that a range no application problem to potassium titanate particles of the present invention may coexist small amount TiO 2 produced by thermal decomposition of TiO 2, potassium titanate unreacted with K source . Furthermore, secondary particles in which primary particles are aggregated may be included.
本発明のチタン酸カリウムは粒子である。又は、扁平で配向し易い特性を持つ。従って均一な摺動面を形成し、ブレーキ材等として優れた摺動特性を有する。また、プラスチック等に配合すれば寸法精度が高く、剛性の向上や表面平滑性の付与等精密成型品等として適している。また、繊維状のチタン酸カリウムに比べ高配合が可能なこと等の特性を生かした補強性を必要としない分野への応用が期待される。 The potassium titanate of the present invention is a particle. Or it has the characteristic of being flat and easily oriented. Therefore, it forms a uniform sliding surface and has excellent sliding characteristics as a brake material or the like. Moreover, if it mix | blends with a plastic etc., a dimensional accuracy is high, and it is suitable as precision molding goods, such as an improvement in rigidity and provision of surface smoothness. Moreover, application to the field | area which does not require the reinforcement | strengthening which utilized the characteristics of being able to mix | blend high compared with fibrous potassium titanate etc. is anticipated.
本発明によれば長径が２μｍ未満のチタン酸カリウム粒子が提供される。この粒子は長径／短径比も小さく、人体への悪影響がないものであり、吸入性繊維を含まないので、安全に各種用途に用いることができる。 According to the present invention, potassium titanate particles having a major axis of less than 2 μm are provided. These particles have a small major axis / minor axis ratio, have no adverse effects on the human body, and do not contain inhalable fibers, so they can be safely used for various applications.
長径／短径比の大きい粒子が、一般的に繊維状、針状、ウィスカー等と表現されているが、従来、長径／短径比の具体的な数値でその定義はされていない。そこで、本発明では安全性と生産性のバランスで長径／短径比を５未満とした。また長径／短径比を３未満、２未満で定義して本発明の粒子形状分布の指標とした。 Particles having a large major axis / minor axis ratio are generally expressed as fibers, needles, whiskers, or the like, but conventionally, the specific value of the major axis / minor axis ratio has not been defined. Therefore, in the present invention, the major axis / minor axis ratio is set to less than 5 in order to balance safety and productivity. The major axis / minor axis ratio was defined as less than 3 and less than 2, and was used as an index of the particle shape distribution of the present invention.
長径２μｍ未満に注目した理由はマクロ的には繊維による人体への悪影響に対する疑念を回避するためである。例えば、中皮腫患者の肺の中にあった石綿小体をＳＥＭ（走査型電子顕微鏡）で見たものが発表されている。中皮腫、肺ガンといった悪性腫瘍と石綿との関係や発ガンのメカニズムは未だ解明されていないが、最もポピュラーな考え方として、次のものがある。石綿が肺胞に到達すると、マクロファージ（貧食細胞）という異物退治の細胞が動員され、石綿を飲み込みタンパク質分解酸素を分泌して無害化しようと働く。ところが、３〜５μｍほどのマクロファージはそれより大きな繊維長を有する石綿を飲み込むことができず、逆に膜が破られてしまう。すると、タンパク質分解酸素が周囲に漏れ始めタンパク質を成分とする肺胞細胞を破壊して炎症を生ずると云われている。一方、繊維性の低い粒子はたとえ肺胞に到達しても長径が１μｍ以下であれば呼気と共に体外に排出されると云われている。従って、本発明では長径が２μｍ未満、より好ましくは１μｍ未満のチタン酸カリウムであって、長径／短径比の小さい粒子を提供するものである。 The reason for paying attention to the major axis of less than 2 μm is to avoid the suspicion of adverse effects on the human body caused by the fibers. For example, an asbestos corpuscle found in the lungs of a mesothelioma patient is observed with an SEM (scanning electron microscope). The relationship between malignant tumors such as mesothelioma and lung cancer and asbestos and the mechanism of carcinogenesis have not yet been elucidated, but the most popular idea is as follows. When the asbestos reaches the alveoli, a foreign body extermination cell called macrophage (phagocytic cell) is mobilized, and it works by swallowing it and secreting proteolytic oxygen to make it harmless. However, macrophages of about 3 to 5 μm cannot swallow asbestos having a fiber length larger than that, and the membrane is broken. Then, it is said that proteolytic oxygen begins to leak to the surroundings, destroying alveolar cells containing the protein as components, and causing inflammation. On the other hand, it is said that even if the particles having low fibrous properties reach the alveoli, they are discharged out of the body with exhalation if the major axis is 1 μm or less. Therefore, the present invention provides a potassium titanate having a major axis of less than 2 μm, more preferably less than 1 μm, and having a small major axis / minor axis ratio.
従来の繊維状のチタン酸カリウムが呼吸器系などの健康に影響を生ずる可能性については明らかではないが、繊維性が不要な用途に用いる場合には、危険な繊維のサイズとして考えられる吸入性繊維は無いことが望ましい。 Although it is not clear that conventional fibrous potassium titanate may affect the health of the respiratory system, etc., when used in applications that do not require fiber, inhalability is considered as a dangerous fiber size It is desirable that there is no fiber.
また、厚さの薄い扁平な形状の粒子から成るチタン酸カリウムも同様に吸入性繊維ではないので好適である。 Further, potassium titanate composed of thin particles having a flat shape is also preferable because it is not an inhalable fiber.
チタン酸カリウムは、高白色度、低モース硬度、低熱伝導率、高屈折率といった物性を持ち、耐熱性、耐薬品性、摺動特性に優れる物質としての特性を有している。従って、補強材としての用途以外に、プラスチック、摩擦材、塗料、紙等への添加剤や潤滑剤、耐熱材、断熱材、電気絶縁材、イオン交換体、触媒等として利用することもできる。更に、繊維状粉末が、嵩高く流動性が悪く扱いにくいのに対し、本発明のチタン酸カリウムは、これらの欠点が改良されている点で、適用範囲は広い。その適用において、目的に沿うよう、カップリング処理等の表面処理を施すこともでき、また、必要に応じ造粒することも可能である。 Potassium titanate has physical properties such as high whiteness, low Mohs hardness, low thermal conductivity, and high refractive index, and has properties as a substance excellent in heat resistance, chemical resistance, and sliding properties. Therefore, in addition to the use as a reinforcing material, it can also be used as an additive or lubricant for plastics, friction materials, paints, paper, etc., heat resistant materials, heat insulating materials, electrical insulating materials, ion exchangers, catalysts, and the like. Furthermore, while the fibrous powder is bulky and poor in fluidity and difficult to handle, the potassium titanate of the present invention has a wide range of applications in that these drawbacks are improved. In the application, a surface treatment such as a coupling treatment can be applied to meet the purpose, and granulation can be performed as necessary.
チタン酸カリウム粒子は、プラスチック等に配合することによって、耐摩擦摩耗特性を付与するため、摺動部品等の用途に適している。 Potassium titanate particles are suitable for applications such as sliding parts because they impart frictional wear resistance properties when blended with plastics.
ブレーキ等の摩擦材に用いた場合には、従来のチタン酸カリウム繊維を用いるよりも、摩擦係数が安定する等のすぐれた摩擦性能を発揮することが見い出されている。 When used for a friction material such as a brake, it has been found that it exhibits superior friction performance such as stabilization of the friction coefficient, compared to the conventional potassium titanate fiber.
Ｋ2ＣＯ3とＴｉＯ2に加えて、Ｋ以外のアルカリ金属を少量加えた混合物の配合割合、焼成条件を変えることによって、粒子形状や分布の異なる焼成物を得た。次いで、それぞれの焼成物に水を加えてスラリー化し、更にＨＣｌを加えてＫ+イオンを溶出させることによってＴｉＯ2／Ｋ2Ｏモル比を調整した後、熱処理を加え、Ｋ2Ｏ・８ＴｉＯ2粒子を得た。 In addition to K 2 CO 3 and TiO 2 , a mixture obtained by adding a small amount of an alkali metal other than K and a firing condition were changed to obtain fired products having different particle shapes and distributions. Next, water was added to each fired product to form a slurry, and HCl was further added to elute K + ions to adjust the TiO 2 / K 2 O molar ratio, followed by heat treatment, and K 2 O · 8TiO 2. Particles were obtained.
それぞれ得られたＫ2Ｏ・８ＴｉＯ2微粒子を化学分析すると、Ｋ以外のアルカリ金属量は、Ｒ2Ｏで３ｗｔ％以下（Ｒ：アルカリ金属）であった。 When the K 2 O · 8TiO 2 fine particles obtained were chemically analyzed, the amount of alkali metal other than K was 3 wt% or less (R: alkali metal) in R 2 O.
更にＫ2Ｏ・８ＴｉＯ2微粒子の電子顕微鏡画像を解析処理し、個々の粒子の長径と短径の寸法及び長径／短径比を求め、長径／短径比が３未満と２未満の個数割合、及びそれぞれの最小値、最大値、平均値を調べた。 Further, an electron microscope image of K 2 O · 8TiO 2 fine particles is analyzed and processed to determine the major axis and minor axis dimensions and the major axis / minor axis ratio of each particle, and the ratio of the major axis / minor axis ratio is less than 3 and less than 2. The minimum value, maximum value, and average value of each were examined.
また、水中で超音波分散処理し、フランホーファ回折とミー散乱を測定原理とするレーザ式の粒度分布測定装置により粒度分布を測定し、累積篩下１００％径（重量％）と５０％径（重量％）を求めた。 In addition, ultrasonic dispersion treatment is performed in water, and the particle size distribution is measured with a laser-type particle size distribution measuring device based on the principle of Franhofer diffraction and Mie scattering. The 100% diameter (weight%) and 50% diameter (weight) %).
Ｘ線回折測定はＤＳ＝１°、ＳＳ＝１°、ＲＳ＝０．３ｍｍのスリットを用い、ＣｕＫａ線で測定した。Ｋ2Ｏ・８ＴｉＯ2の（２００）／（０２０）の回折強度比を求めた。結果を表１に示す。 X-ray diffraction measurement was performed with CuKa line using a slit of DS = 1 °, SS = 1 °, and RS = 0.3 mm. The (200) / (020) diffraction intensity ratio of K 2 O · 8TiO 2 was determined. The results are shown in Table 1.
実施例１〜３で得られたチタン酸カリウムの粒子形状は、表１に示すように長径は最大で０．７４〜１．７３μｍであり、長径／短径比は最大で２．９５〜４．５６である。また長径／短径比５未満の粒子の個数割合は１００％、３未満の粒子個数割合は９８．７〜１００％、２未満の粒子個数割合は９３．８〜９８．０％である。（２００）／（０２０）Ｘ線回折強度比は０．６５〜２．５４であった。 As shown in Table 1, the major axis of the potassium titanate particles obtained in Examples 1 to 3 has a major axis of 0.74 to 1.73 μm at the maximum and the major axis / minor axis ratio of 2.95 to 4 at the maximum. .56. The ratio of the number of particles having a major axis / minor axis ratio of less than 5 is 100%, the ratio of the number of particles less than 3 is 98.7 to 100%, and the ratio of the number of particles less than 2 is 93.8 to 98.0%. The (200) / (020) X-ray diffraction intensity ratio was 0.65 to 2.54.
図１は実施例１で得られた本発明のチタン酸カリウム粒子の１０，０００倍の代表的な顕微鏡写真、比較として示した図２は従来のチタン酸カリウムの１，５００倍の顕微鏡写真である。図２に示す従来のチタン酸カリウムは、繊維形状を呈しているのに対し、図１に示す実施例の粒子は、長径が１μｍ以下でその大部分は長径／短径比が２以下である。また、厚さが薄い扁平な粒子形状が観察される。 FIG. 1 is a representative photomicrograph of 10,000 times the potassium titanate particles of the present invention obtained in Example 1, and FIG. 2 shown as a comparison is a photomicrograph of 1,500 times that of conventional potassium titanate. is there. The conventional potassium titanate shown in FIG. 2 has a fiber shape, whereas the particles of the example shown in FIG. 1 have a major axis of 1 μm or less and most of them have a major axis / minor axis ratio of 2 or less. . In addition, a flat particle shape with a small thickness is observed.
図３は、本発明の実施例１の粒子についてその短径と長径の関係をプロットしたものである。図中に長径／短径比＝１，２，３，４，５の線を記入した。長径／短径比が５を越える粒子は皆無である。なお長径５μｍ以上、短径３μｍ以下、長径／短径比が３以上の有害繊維とされる領域を併せて示した。 FIG. 3 is a plot of the relationship between the minor axis and the major axis of the particles of Example 1 of the present invention. In the figure, lines of major axis / minor axis ratio = 1, 2, 3, 4, 5 were entered. There are no particles having a major axis / minor axis ratio exceeding 5. In addition, the area | region made into a harmful fiber whose major axis is 5 micrometers or more, minor axis 3 micrometers or less, and a major axis / minor axis ratio is 3 or more was shown collectively.
図１、図２に示す粒子のＸ線回折パターンを図４に示した。従来の８チタン酸カリウムは、鋭い回折ピークを示すのに対し本発明の８チタン酸カリウムは低結晶性である。（２００）／（０２０）回折強度比は、従来品では６．３を示したが、実施例１では０．６５である。実施例２、３においても（２００）／（０２０）回折強度比は、３以下である。 The X-ray diffraction patterns of the particles shown in FIGS. 1 and 2 are shown in FIG. The conventional potassium 8 titanate shows a sharp diffraction peak, whereas the 8 potassium titanate of the present invention has low crystallinity. The (200) / (020) diffraction intensity ratio was 6.3 in the conventional product, but 0.65 in Example 1. In Examples 2 and 3, the (200) / (020) diffraction intensity ratio is 3 or less.
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