JP5097408B2 - Rutile-type titanium oxide particles and method for producing the same - Google Patents
Rutile-type titanium oxide particles and method for producing the same Download PDFInfo
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本発明は、ルチル型酸化チタン粒子及びその製造方法、特に、高アスペクト比を有し、単結晶であるルチル型酸化チタン粒子及びその製造方法に関する。 The present invention relates to rutile-type titanium oxide particles and a method for producing the same, and more particularly to rutile-type titanium oxide particles having a high aspect ratio and being a single crystal and a method for producing the same.
酸化チタンは、正の複屈折性を有するため、例えば、光学用途等の複屈折の調節が要請される用途での応用が期待される。ここで、前記複屈折の調節を行なうためには、例えば、粒子を含む高分子膜を溶液製膜する場合には、乾燥過程における溶液の蒸散過程において粒子を面内に配向させるために、粒子はｎｍサイズであって、且つ、針状、棒状、紡錘状、平板等の球状でない形態であることが必要である。あるいは、粒子を含む膜は、その製膜方法によらず、製膜時に延伸されるため、粒子はｎｍサイズであって、且つ、針状、棒状、紡錘状等の高アスペクト比であることが必要である。 Titanium oxide has a positive birefringence, and is expected to be applied in applications where birefringence adjustment is required, such as optical applications. Here, in order to adjust the birefringence, for example, when a polymer film containing particles is formed into a solution, in order to orient the particles in the plane in the evaporation process of the solution in the drying process, It is necessary to have a nanometer size and a non-spherical shape such as a needle shape, a rod shape, a spindle shape, or a flat plate. Alternatively, since the film containing particles is stretched during film formation regardless of the film forming method, the particles have a nanometer size and a high aspect ratio such as a needle shape, a rod shape, or a spindle shape. is necessary.
前記酸化チタンの結晶型には、アナターゼ型、ルチル型、及びブルッカイト型が存在する。このうち、ルチル型粒子を得る方法としては、例えば、アナターゼ型粒子を約９００℃にて加熱焼成する方法が知られている。しかし、この方法では、アナターゼ型粒子の段階の粒子形態やサイズを維持したルチル型粒子を得ることが難しいことから、長径がｎｍサイズのルチル型粒子を得ることも困難である。また、この方法では、一旦アナターゼ型粒子を得てからでなければルチル型粒子を得ることができず、工程が煩雑となる。 The crystal form of the titanium oxide includes an anatase type, a rutile type, and a brookite type. Among these, as a method for obtaining rutile type particles, for example, a method in which anatase type particles are heated and fired at about 900 ° C. is known. However, with this method, it is difficult to obtain rutile type particles that maintain the particle form and size at the stage of anatase type particles, and it is therefore difficult to obtain rutile type particles having a major axis of nm size. Further, in this method, rutile type particles cannot be obtained unless anatase type particles are once obtained, and the process becomes complicated.
一方、アナターゼ型粒子を介さずに、ルチル型粒子を直接得る方法としては、気相中での熱分解法が知られているが(特許文献１参照)、この方法では、球状等の低アスペクト比のルチル型粒子が得られてしまい、針状、棒状、紡錘状等の高アスペクト比のルチル型酸化チタン粒子を得ることができない。
また、アナターゼ型酸化チタン粒子については、針状、棒状、紡錘状等の粒子が得られた旨の報告があるが（非特許文献１参照）、ルチル型酸化チタン粒子については、そのような報告は見出されていない。
On the other hand, as a method for directly obtaining rutile-type particles without using anatase-type particles, a thermal decomposition method in a gas phase is known (see Patent Document 1). In other words, rutile type particles having a high aspect ratio such as needles, rods, and spindles cannot be obtained.
As for anatase-type titanium oxide particles, there are reports that particles such as needles, rods, and spindles have been obtained (see Non-Patent Document 1), but for rutile-type titanium oxide particles, such reports are available. Has not been found.
したがって、アナターゼ型酸化チタン粒子を高温焼成する方法以外で形成可能であり、高アスペクト比を有し、複屈折の調節が要請される用途で応用し得るルチル型酸化チタン粒子及びその製造方法は未だ提供されておらず、その開発が強く望まれているのが現状である。
一方で、非特許文献２のようにルチル型の粒子を直接形成させる方法も存在するが、得られる粒子は球状であって、高分子膜中に添加した場合に、針状や棒状で実現できる配向性付与（粒子のある結晶軸をある方向に並べること）ができない。
Therefore, rutile type titanium oxide particles that can be formed by methods other than the method of firing anatase type titanium oxide particles at a high temperature, have a high aspect ratio, and can be applied in applications requiring adjustment of birefringence, and methods for producing the same are still available. It is not provided and the development is strongly desired.
On the other hand, there is a method of directly forming rutile-type particles as in Non-Patent Document 2, but the obtained particles are spherical and can be realized in a needle shape or a rod shape when added to a polymer film. Orientation cannot be imparted (the crystal axes with particles are aligned in a certain direction).
また、特許文献２、特許文献３（比較例２）、及び特許文献４（比較例２）等においては、高アスペクト比を有するルチル型酸化チタン粒子が知られているが、それぞれ以下のような問題点がある。
特許文献２では、酸化錫（ＳｎＯ２）を含む粒子となってしまうことから、高純度なルチル粒子とはならない。
特許文献３（比較例２）では、小さな粒子が凝集して、多結晶の針状粒子が形成されているので、針状や棒状粒子の長軸方向が、結晶(単位格子)のｃ軸方向に一致しているとは限らない。そのため、このような粒子を高分子膜中に添加し、何らかの配向を実現しても、前記複屈折の調節を行なうことができず、あるいは、調節が行なえたとしてもより多くの粒子を添加する必要がある。
In Patent Document 2, Patent Document 3 (Comparative Example 2), Patent Document 4 (Comparative Example 2) and the like, rutile-type titanium oxide particles having a high aspect ratio are known. There is a problem.
In Patent Document 2, since it becomes particles containing tin oxide (SnO 2), not a high purity rutile particles.
In Patent Document 3 (Comparative Example 2), since small particles aggregate to form polycrystalline needle-like particles, the major axis direction of the needle-like or rod-like particles is the c-axis direction of the crystal (unit cell). Does not necessarily match. Therefore, even if such particles are added to the polymer film and some orientation is realized, the birefringence cannot be adjusted, or even if the adjustment can be made, more particles are added. There is a need.
さらに、特許文献４（比較例２）では、粒子の顕微鏡写真とその比表面積の値から多結晶粒子である可能性が高い。多結晶粒子の場合、上述のように、針状や棒状粒子の長軸方向が、結晶(単位格子)のｃ軸方向に一致しているとは限らない。そのため、このような粒子を高分子膜中に添加し、何らかの配向を実現しても、前記複屈折の調節を行なうことができず、あるいは、調節が行えたとしてもより多くの粒子を添加する必要がある。 Furthermore, in Patent Document 4 (Comparative Example 2), there is a high possibility that the particles are polycrystalline particles from the micrograph of the particles and the value of the specific surface area. In the case of polycrystalline particles, as described above, the major axis direction of needle-like or rod-like particles does not always coincide with the c-axis direction of the crystal (unit cell). Therefore, even if such particles are added to the polymer film and some orientation is realized, the birefringence cannot be adjusted, or even if the adjustment can be made, more particles are added. There is a need.
本発明は、従来における前記問題を解決し、以下の目的を達成することを課題とする。即ち、本発明は、アナターゼ型酸化チタン粒子を高温焼成する方法以外で簡単に形成可能であり、単結晶で高アスペクト比を有し、複屈折の調節が要請される用途（例えば、ＬＣＤやプロジェクタ用の位相差板、位相差フィルム）で応用し得るルチル型酸化チタン粒子及びその製造方法を提供することを目的とする。 An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention can be easily formed by a method other than the method of firing anatase-type titanium oxide particles at a high temperature, is a single crystal, has a high aspect ratio, and is required to adjust birefringence (for example, an LCD or a projector). It is an object of the present invention to provide rutile type titanium oxide particles and a method for producing the same that can be applied in a phase difference plate and a phase difference film.
前記課題を解決するための手段は以下の通りである。即ち、
＜１＞ 平均最大短径が５〜５０ｎｍ、且つ平均最大長径が３０〜３００ｎｍであり、単結晶であることを特徴とするルチル型酸化チタン粒子である。
＜２＞ 平均アスペクト比が２以上である前記＜１＞１に記載のルチル型酸化チタン粒子である。
＜３＞ 過塩素酸存在下の反応溶液中で形成することを特徴とするルチル型酸化チタン粒子の製造方法である。
＜４＞ 前記反応溶液の温度が６０℃以下であることを特徴とする前記＜３＞に記載のルチル型酸化チタン粒子の製造方法である。
＜５＞ 酸化チタン原料として、前記反応溶液中にチタニウムイソプロポキシドを含むことを特徴とする前記＜３＞又は＜４＞に記載のルチル型酸化チタン粒子の製造方法である。
＜６＞ 前記＜３＞〜＜５＞のいずれかに記載の製造方法によって得られるルチル型酸化チタン粒子である。
＜７＞ 平均最大短径が５〜５０ｎｍ、平均最大長径が３０〜３００ｎｍであることを特徴とする前記＜６＞に記載のルチル型酸化チタン粒子である。
＜８＞ 単結晶であることを特徴とする前記＜６＞又は＜７＞に記載のルチル型酸化チタン粒子である。
Means for solving the above-mentioned problems are as follows. That is,
<1> Rutile-type titanium oxide particles having an average maximum minor axis of 5 to 50 nm, an average maximum major axis of 30 to 300 nm, and a single crystal.
<2> The rutile-type titanium oxide particles according to <1> 1, wherein the average aspect ratio is 2 or more.
<3> A method for producing rutile-type titanium oxide particles, which is formed in a reaction solution in the presence of perchloric acid.
<4> The method for producing rutile-type titanium oxide particles according to <3>, wherein the temperature of the reaction solution is 60 ° C. or lower.
<5> The method for producing rutile-type titanium oxide particles according to <3> or <4>, wherein the reaction solution contains titanium isopropoxide as a titanium oxide raw material.
<6> Rutile-type titanium oxide particles obtained by the production method according to any one of <3> to <5>.
<7> The rutile-type titanium oxide particles according to <6>, wherein the average maximum minor axis is 5 to 50 nm and the average maximum major axis is 30 to 300 nm.
<8> The rutile-type titanium oxide particle according to <6> or <7>, which is a single crystal.
本発明によると、従来における前記問題を解決することができ、アナターゼ型酸化チタン粒子を高温焼成する方法以外で簡単に形成可能であり、単結晶で高アスペクト比を有し、複屈折の調節が要請される用途で応用し得るルチル型酸化チタン粒子及びその製造方法を提供することができる。 According to the present invention, the above-mentioned problems in the prior art can be solved, and the anatase-type titanium oxide particles can be easily formed by a method other than the high-temperature firing method, have a high aspect ratio with a single crystal, and can adjust birefringence. It is possible to provide rutile-type titanium oxide particles that can be applied for required uses and a method for producing the same.
（ルチル型酸化チタン粒子及びその製造方法）
本発明のルチル型酸化チタン粒子は、平均最大短径が５〜５０ｎｍ、且つ平均最大長径が３０〜３００ｎｍであり、単結晶であることを特徴とする。なお、本発明のルチル型酸化チタン粒子の製造方法は、本発明の前記ルチル型酸化チタン粒子の説明を通じて明らかにする。
「単結晶」とは、結晶のどの位置であっても、結晶軸の方向が変わらないものをいう。そして、単結晶の集合体が多結晶である。
単結晶と多結晶の判別方法としては、以下の方法が挙げられる。すなわち、透過型電子顕微鏡によって観察中の粒子を選択し、その粒子に対して、該顕微鏡に具備されている電子線回折装置によって回折像をとることにより、その回折パターンがスポット状になれば単結晶、リング状になれば多結晶と判別することができる。
(Rutyl-type titanium oxide particles and production method thereof)
The rutile-type titanium oxide particles of the present invention have an average maximum minor axis of 5 to 50 nm, an average maximum major axis of 30 to 300 nm, and are single crystals. In addition, the manufacturing method of the rutile type titanium oxide particle of this invention is clarified through description of the said rutile type titanium oxide particle of this invention.
“Single crystal” refers to a crystal whose direction of crystal axis does not change at any position of the crystal. The aggregate of single crystals is polycrystalline.
As a method for discriminating between a single crystal and a polycrystal, the following methods may be mentioned. That is, by selecting a particle under observation with a transmission electron microscope and taking a diffraction image of the particle with an electron beam diffractometer provided in the microscope, if the diffraction pattern becomes a spot shape, If it becomes a crystal or ring shape, it can be identified as a polycrystal.
前記酸化チタン粒子が、ルチル型であるかアナターゼ型であるかは、例えば、Ｘ線回折（ＸＲＤ）にて得られた粒子の結晶相を同定することにより確認することができる。
前記ルチル型酸化チタン粒子の形状としては、平均最大長径及び平均最大短径が上記範囲内であれば特に制限はないが、例えば、針状、棒状、紡錘状等であることが好ましい。
Whether the titanium oxide particles are rutile or anatase can be confirmed, for example, by identifying the crystal phase of the particles obtained by X-ray diffraction (XRD).
The shape of the rutile-type titanium oxide particles is not particularly limited as long as the average maximum major axis and the average maximum minor axis are within the above ranges, but for example, a needle shape, a rod shape, a spindle shape and the like are preferable.
本発明において、前記ルチル型酸化チタン粒子の平均最大短径は、上述のように５〜５０ｎｍであるが、５〜３０ｎｍであることが好ましく、５〜２０ｎｍであることがより好ましい。前記ルチル型酸化チタン粒子の平均最大長径は、上述のように３０〜３００ｎｍであるが、３０〜２００ｎｍであることが好ましく、３０〜１００ｎｍであることがより好ましい。前記平均最大短径あるいは平均最大長径が上記範囲外であると、例えばこの粒子を樹脂中に分散させた場合等に、その透明性が大きく低下することがある。 In the present invention, the average maximum minor axis of the rutile-type titanium oxide particles is 5 to 50 nm as described above, preferably 5 to 30 nm, and more preferably 5 to 20 nm. The average maximum major axis of the rutile-type titanium oxide particles is 30 to 300 nm as described above, but is preferably 30 to 200 nm, and more preferably 30 to 100 nm. When the average maximum minor axis or the average maximum major axis is out of the above range, for example, when the particles are dispersed in a resin, the transparency may be greatly lowered.
前記ルチル型酸化チタン粒子の短径は、例えば、得られたルチル型酸化チタン粒子を透過型電子顕微鏡（ＴＥＭ）にて観察し、撮影した粒子写真をスキャナーで取り込んで画像ファイルとして保存し、この保存した画像ファイル（電子ファイル）に対し、株式会社マウンテック製、画像解析式粒度分布ソフトウェア「Ｍａｃ−Ｖｉｅｗ」Ｖｅｒ．３を用い、観察できる粒子を取り込み、更にこのソフトによって計算されたその短手方向（幅）の最も大きい箇所の径（最大短径）を平均化して求めることができる。
前記ルチル型酸化チタン粒子の長径は、同様にして長手方向の最も大きい箇所の径（最大長径）を平均化して求めることができる。
The short diameter of the rutile-type titanium oxide particles can be determined by, for example, observing the obtained rutile-type titanium oxide particles with a transmission electron microscope (TEM), capturing the photographed particle photograph with a scanner, and saving the image file. For the saved image file (electronic file), image analysis type particle size distribution software “Mac-View” Ver. 3 can be obtained by taking in particles that can be observed and averaging the diameter (maximum short diameter) of the largest portion in the short direction (width) calculated by this software.
Similarly, the major axis of the rutile-type titanium oxide particles can be determined by averaging the diameter of the largest part in the longitudinal direction (maximum major axis).
本発明において、前記ルチル型酸化チタン粒子のアスペクト比は、好ましい形状の粒子を得る観点から、２以上であることが好ましく、４〜１０であることがより好ましい。前記アスペクト比が２未満であると、粒子が粒状又は球状に近くなり、例えば樹脂中に分散させた場合に、分子配向に伴って粒子配向が発現する確率が減少乃至ゼロとなってしまうことがある。前記アスペクト比は、例えば、平均最大長径／平均最大短径により求めることができる。 In the present invention, the aspect ratio of the rutile-type titanium oxide particles is preferably 2 or more, and more preferably 4 to 10 from the viewpoint of obtaining particles having a preferable shape. When the aspect ratio is less than 2, the particles are almost granular or spherical, and when dispersed in a resin, for example, the probability that the particle orientation appears with the molecular orientation may be reduced to zero. is there. The aspect ratio can be obtained by, for example, average maximum major axis / average maximum minor axis.
光学用途に応用した場合に、光散乱による透過率減少を起こす粒子の含有率を下げ、実質的に散乱の少ない状態を実現する観点から、前記ルチル型酸化チタン粒子の径のバラツキとしては、短径及び長径のいずれにおいても、変動係数が０．４以下であることが好ましく、０．３以下であることがより好ましい。前記変動係数が、０．４を超えると、平均値より長い粒子の混合比が増加し、例えば樹脂中に分散させた場合に、該樹脂の光透過率が低下することがある。 From the viewpoint of reducing the content of particles that cause a decrease in transmittance due to light scattering and realizing a state of substantially less scattering when applied to optical applications, the variation in the diameter of the rutile titanium oxide particles is short. In any of the diameter and the major axis, the coefficient of variation is preferably 0.4 or less, and more preferably 0.3 or less. If the coefficient of variation exceeds 0.4, the mixing ratio of particles longer than the average value increases. For example, when dispersed in a resin, the light transmittance of the resin may decrease.
前記変動係数とは、前記平均最大短径又は前記平均最大短径に対する短径又は長径の標準偏差の比で表され、下記数式（１）で求められる。
前記ｎの値は、１００以上と定義するが、より大きい方が好ましく、２００以上であることがより好ましい。前記ｎの値が、１００未満となると、粒子の分散を正確に反映できなくなることがある。変動係数を百分率で表示する場合には、上記数式（１）の値を１００倍した値として表示することができる。例えば、前記変動係数の値が、０．４０以下である場合には、百分率表示では、４０％以下と表示することができる。 The value of n is defined as 100 or more, but is preferably larger and more preferably 200 or more. If the value of n is less than 100, the dispersion of particles may not be accurately reflected. When the coefficient of variation is displayed as a percentage, it can be displayed as a value obtained by multiplying the value of Equation (1) by 100. For example, when the value of the variation coefficient is 0.40 or less, 40% or less can be displayed in percentage display.
前記変動係数は、例えば、分散させた粒子を透過型電子顕微鏡（ＴＥＭ）にて観察し、撮影した粒子写真をスキャナーで取り込んで画像ファイルとして保存し、この保存した画像ファイル情報を、株式会社マウンテック製、画像解析式粒度分布測定ソフトウェア「Ｍａｃ−Ｖｉｅｗ」Ｖｅｒ．３を用いて１粒子ごとに測定し、集計することで求めることができる。 The coefficient of variation is obtained by, for example, observing dispersed particles with a transmission electron microscope (TEM), capturing a photograph of the photographed particles with a scanner, and saving the image file as an image file. Manufactured by Image Analysis type particle size distribution measurement software “Mac-View” Ver. It can be obtained by measuring every particle using 3 and counting.
−反応溶液−
前記ルチル型酸化チタン粒子は、酸性の反応用液中で形成される。
前記ルチル型酸化チタン粒子が、酸性の反応溶液中で形成されたことは、例えば、得られた粒子を水等の溶媒中に再分散したときのｐＨ測定等により分析することができる。
前記反応溶液のｐＨとしては、酸性、すなわちｐＨ７未満であればよいが、酸化チタン粒子の溶解度曲線（溶解度のｐＨ依存性）からわかるように、過飽和度の小さな領域での合成が可能な領域で、高アスペクト比の形態を有する粒子を容易に得られる観点から、１．５以下であることが好ましく、１以下であることがより好ましい。
前記反応溶液の温度としては、特に制限はなく、目的に応じて適宜選択することができるが、簡易な設備でも製造可能とする観点からは、６０℃未満であることが好ましく、４０℃未満であることがより好ましい。
-Reaction solution-
The rutile titanium oxide particles are formed in an acidic reaction solution.
The formation of the rutile-type titanium oxide particles in the acidic reaction solution can be analyzed, for example, by measuring pH when the obtained particles are redispersed in a solvent such as water.
The pH of the reaction solution may be acidic, i.e., less than pH 7. However, as can be seen from the solubility curve of titanium oxide particles (pH dependence of solubility), the reaction solution can be synthesized in a region where the degree of supersaturation is small. From the viewpoint of easily obtaining particles having a high aspect ratio, it is preferably 1.5 or less, more preferably 1 or less.
There is no restriction | limiting in particular as temperature of the said reaction solution, Although it can select suitably according to the objective, It is preferable that it is less than 60 degreeC, and less than 40 degreeC from a viewpoint which enables manufacture also with simple equipment. More preferably.
前記反応溶液としては、好ましいｐＨとする観点からは、強酸を含むことが好ましい。前記強酸としては、特に制限はなく、公知のものを適宜選択して用いることができるが、本発明の粒子を得やすい観点から、過塩素酸が好適に用いられる。
前記強酸の反応溶液中における含有量としては、例えば、０．５〜１．５Ｍであることが好ましく、０．５〜０．９Ｍであることがより好ましい。
The reaction solution preferably contains a strong acid from the viewpoint of a preferable pH. There is no restriction | limiting in particular as said strong acid, Although a well-known thing can be selected and used suitably, Perchloric acid is used suitably from a viewpoint which is easy to obtain the particle | grains of this invention.
As content in the reaction solution of the said strong acid, it is preferable that it is 0.5-1.5M, for example, and it is more preferable that it is 0.5-0.9M.
前記反応溶液中に含まれるルチル型酸化チタンの原料としては、特に制限はなく、例えば、硫酸チタニル、四塩化チタン、チタニウムイソプロポキシド（ＴＩＰＯ）等が挙げられるが、本発明では、チタニウムイソプロポキシドが好適に用いられる。
反応溶液中における前記酸化チタン原料の配合量は、例えば、０．１０〜０．８０Ｍであることが好ましく、０．１０〜０．５０Ｍであることがより好ましい。
The raw material of the rutile type titanium oxide contained in the reaction solution is not particularly limited, and examples thereof include titanyl sulfate, titanium tetrachloride, titanium isopropoxide (TIPO), etc. In the present invention, titanium isopropoxy is used. Is preferably used.
The compounding amount of the titanium oxide raw material in the reaction solution is, for example, preferably 0.10 to 0.80M, and more preferably 0.10 to 0.50M.
−製造例−
本発明のルチル型酸化チタン粒子の具体的な製造例としては、これに限定されないが、以下の方法が挙げられる。
過塩素酸水溶液中に、これと同体積のチタニウムイソプロポキシド水溶液を添加し、攪拌する。この溶液を１００℃未満、好ましくは６０℃未満に保った恒温槽中で、その温度に応じて数時間〜１０日間静置し反応させる。得られた溶液を、遠心分離にかけ、回収できた沈殿を水洗、乾燥後、粉砕する。
-Production example-
Specific examples of production of the rutile-type titanium oxide particles of the present invention include, but are not limited to, the following methods.
The same volume of titanium isopropoxide aqueous solution is added to the perchloric acid aqueous solution and stirred. This solution is allowed to stand and react for several hours to 10 days depending on the temperature in a thermostat kept at less than 100 ° C, preferably less than 60 ° C. The obtained solution is centrifuged, and the recovered precipitate is washed with water, dried and then pulverized.
−用途−
本発明のルチル型酸化チタンは、上述のように、平均最大短径５〜５０ｎｍ、平均最大長径３０〜３００ｎｍであり、高アスペクト比を有するｎｍサイズである。このため、正の複屈折性を有する酸化チタンの性質を利用して、複屈折の調節が要請される用途（例えば、ＬＣＤやプロジェクタ用の位相差板、位相差フィルム）で好適に用いることができる。具体的には、光学用途において、例えば、偏向特性が重要で高精度が要求される光学素子を構成する樹脂において使用することができる。
-Application-
As described above, the rutile-type titanium oxide of the present invention has an average maximum minor axis of 5 to 50 nm, an average maximum major axis of 30 to 300 nm, and a nm size having a high aspect ratio. For this reason, using the property of titanium oxide having positive birefringence, it can be suitably used in applications requiring adjustment of birefringence (for example, retardation plates and retardation films for LCDs and projectors). it can. Specifically, in an optical application, for example, it can be used in a resin constituting an optical element in which deflection characteristics are important and high accuracy is required.
以下、本発明の実施例について説明するが、本発明は下記実施例に何ら限定されるものではない。
初めに、本実施例における平均最大短径、平均最大長径、アスペクト比、及び変動係数の測定方法について、説明する。
−平均最大短径、平均最大長径、アスペクト比、及び変動係数−
前記平均最大短径は、撮影した粒子写真をスキャナーで取り込んで画像ファイルとして保存し、この保存した画像ファイル（電子ファイル）に対し、株式会社マウンテック製、画像解析式粒度分布ソフトウェア「Ｍａｃ−Ｖｉｅｗ」Ｖｅｒ．３を用い、観察できる粒子を取り込み、更にこのソフトによって計算されたその短手方向（幅）の最も大きい箇所の径を、平均化して求める。
Examples of the present invention will be described below, but the present invention is not limited to the following examples.
First, a method for measuring the average maximum minor axis, the average maximum major axis, the aspect ratio, and the coefficient of variation in the present embodiment will be described.
-Average maximum minor axis, average maximum major axis, aspect ratio, and coefficient of variation-
The average maximum minor axis is obtained by taking a photograph of a photographed particle with a scanner and saving it as an image file. For this saved image file (electronic file), image analysis type particle size distribution software “Mac-View” manufactured by Mountec Co., Ltd. Ver. No. 3 is used to take particles that can be observed, and the diameter of the largest portion in the short direction (width) calculated by this software is averaged to obtain.
前記平均最大長径は、前記平均最大短径と同様にして長手方向の最も大きい箇所の径を、平均化して求める。
前記アスペクト比は、平均最大長径／平均最大短径により求める。
前記変動係数は、下記数式（１）により、保存した画像ファイル情報を、株式会社マウンテック製、画像解析式粒度分布測定ソフトウェア「Ｍａｃ−Ｖｉｅｗ」Ｖｅｒ．３を用いて１粒子ごとに測定し、集計することで求める。
The average maximum major axis is obtained by averaging the diameter of the largest part in the longitudinal direction in the same manner as the average maximum minor axis.
The aspect ratio is determined by the average maximum major axis / average maximum minor axis.
The coefficient of variation is calculated using the following mathematical formula (1), and the saved image file information is converted into the image analysis type particle size distribution measurement software “Mac-View” Ver. Measured for each particle using 3 and calculated.
（実施例１）
１．６Ｍの過塩素酸（ＨＣｌＯ４）水溶液中に、同体積の０．５０Ｍのチタニウムイソプロポキシド（関東化学、以下「ＴＩＰＯ」と称す）水溶液を２５℃で添加し、攪拌して反応溶液を得た。得られた反応溶液における各成分の濃度（含有量）は、ＴＩＰＯ：０．２５Ｍ、ＨＣｌＯ４：０．８０Ｍ、ｐＨは０．３０であった。この溶液を２５℃の恒温槽中で、３日間静置して反応させた。反応後のｐＨは、０．２０であった。
得られた溶液を、１０，０００回転で１０分間の遠心分離にかけ、回収できた沈殿を水洗し、一部を透過型電子顕微鏡（ＴＥＭ）にて観察し、５万倍及び１０万倍に拡大した粒子写真をそれぞれ撮影した（図１）。この写真により、上記方法にて平均最大短径、平均最大長径、アスペクト比、及び変動係数を測定したところ、平均最大短径は１４ｎｍ、平均最大長径は１２０ｎｍ、アスペクト比は５．６、短径の変動係数は２５％、長径の変動係数は１８％であった。
Example 1
To a 1.6 M aqueous solution of perchloric acid (HClO 4 ), an equal volume of 0.50 M titanium isopropoxide (Kanto Chemical, hereinafter referred to as “TIPO”) is added at 25 ° C., and the reaction solution is stirred. Got. The concentration (content) of each component in the obtained reaction solution was TIPO: 0.25M, HClO 4 : 0.80M, and pH was 0.30. This solution was allowed to react in a constant temperature bath at 25 ° C. for 3 days. The pH after the reaction was 0.20.
The obtained solution was centrifuged at 10,000 rpm for 10 minutes, the collected precipitate was washed with water, and a part thereof was observed with a transmission electron microscope (TEM) and magnified to 50,000 times and 100,000 times. Each particle photograph was taken (FIG. 1). From this photograph, the average maximum minor axis, the average maximum major axis, the aspect ratio, and the coefficient of variation were measured by the above method. The average maximum minor axis was 14 nm, the average maximum major axis was 120 nm, the aspect ratio was 5.6, and the minor axis. The variation coefficient was 25%, and the variation coefficient of the major axis was 18%.
残りの沈殿を６０℃で乾燥させた後、粉砕し、図４に示すＸ線回折（ＸＲＤ）測定を行った。この結果、ルチル型酸化チタン粒子が得られたことが確認された。さらに、透過型電子顕微鏡観察時に電子線回折像を撮影し、得られたパターンがスポットパターンであったことから、該ルチル型粒子が単結晶粒子であることが確認された。 The remaining precipitate was dried at 60 ° C., pulverized, and X-ray diffraction (XRD) measurement shown in FIG. 4 was performed. As a result, it was confirmed that rutile type titanium oxide particles were obtained. Furthermore, an electron beam diffraction image was taken at the time of observation with a transmission electron microscope, and the obtained pattern was a spot pattern. Thus, it was confirmed that the rutile type particles were single crystal particles.
（実施例２）
１．６Ｍの過塩素酸（ＨＣｌＯ４）水溶液中に、同体積の０．５０Ｍのチタニウムイソプロポキシド（関東化学、以下「ＴＩＰＯ」と称す）水溶液を２５℃で添加し、攪拌して反応溶液を得た。得られた反応溶液における各成分の濃度（含有量）は、ＴＩＰＯ：０．２５Ｍ、ＨＣｌＯ４：０．８０Ｍ、ｐＨは０．３０であった。この溶液を２５℃の恒温槽中で、７日間静置して反応させた。反応後のｐＨは、０．１８であった。
得られた溶液を、１０，０００回転で１０分間の遠心分離にかけ、回収できた沈殿を水洗し、一部を透過型電子顕微鏡（ＴＥＭ）にて観察し、５万倍及び１０万倍に拡大した粒子写真をそれぞれ撮影した（図２）。この写真により、上記方法にて平均最大短径、平均最大長径、アスペクト比、及び変動係数を測定したところ、平均最大短径は１８ｎｍ、平均最大長径は１７８ｎｍ、アスペクト比は５．８、短径の変動係数は１９％、長径の変動係数は２２％であった。
(Example 2)
To a 1.6 M aqueous solution of perchloric acid (HClO 4 ), an equal volume of 0.50 M titanium isopropoxide (Kanto Chemical, hereinafter referred to as “TIPO”) is added at 25 ° C., and the reaction solution is stirred. Got. The concentration (content) of each component in the obtained reaction solution was TIPO: 0.25M, HClO 4 : 0.80M, and pH was 0.30. The solution was allowed to react in a constant temperature bath at 25 ° C. for 7 days. The pH after the reaction was 0.18.
The obtained solution was centrifuged at 10,000 rpm for 10 minutes, the collected precipitate was washed with water, and a part thereof was observed with a transmission electron microscope (TEM) and magnified to 50,000 times and 100,000 times. Each particle photograph was taken (FIG. 2). From this photograph, the average maximum minor axis, average maximum major axis, aspect ratio, and coefficient of variation were measured by the above method. The average maximum minor axis was 18 nm, the average maximum major axis was 178 nm, the aspect ratio was 5.8, and the minor axis. The variation coefficient was 19%, and the variation coefficient of the major axis was 22%.
残りの沈殿を６０℃で乾燥させた後、粉砕し、図４に示すＸ線回折（ＸＲＤ）測定を行った。この結果、ルチル型酸化チタン粒子が得られたことが確認された。さらに、透過型電子顕微鏡観察時に電子線回折像を撮影し、得られたパターンがスポットパターンであったことから、該ルチル型粒子が単結晶粒子であることが確認された。 The remaining precipitate was dried at 60 ° C., pulverized, and X-ray diffraction (XRD) measurement shown in FIG. 4 was performed. As a result, it was confirmed that rutile type titanium oxide particles were obtained. Furthermore, an electron beam diffraction image was taken at the time of observation with a transmission electron microscope, and the obtained pattern was a spot pattern. Thus, it was confirmed that the rutile type particles were single crystal particles.
（実施例３）
１．６Ｍの過塩素酸（ＨＣｌＯ４）水溶液中に、同体積の０．５０Ｍのチタニウムイソプロポキシド（関東化学、以下「ＴＩＰＯ」と称す）水溶液を２５℃で添加し、攪拌して反応溶液を得た。得られた反応溶液における各成分の濃度（含有量）は、ＴＩＰＯ：０．２５Ｍ、ＨＣｌＯ４：０．８０Ｍ、ｐＨは０．３０であった。この溶液を、５０℃の恒温槽中で、３日間静置して反応させた。反応後のｐＨは、０．２３であった。
得られた溶液を、１０，０００回転で１０分間の遠心分離にかけ、回収できた沈殿を水洗し、一部を透過型電子顕微鏡（ＴＥＭ）にて観察し、５万倍及び１０万倍に拡大した粒子写真をそれぞれ撮影した（図３）。この写真により、上記方法にて平均最大短径、平均最大長径、アスペクト比、及び変動係数を測定したところ、平均最大短径は１５ｎｍ、平均最大長径は１６４ｎｍ、アスペクト比は５．５、短径の変動係数は１７％、長径の変動係数は２０％であった。
(Example 3)
To a 1.6 M aqueous solution of perchloric acid (HClO 4 ), an equal volume of 0.50 M titanium isopropoxide (Kanto Chemical, hereinafter referred to as “TIPO”) is added at 25 ° C., and the reaction solution is stirred. Got. The concentration (content) of each component in the obtained reaction solution was TIPO: 0.25M, HClO 4 : 0.80M, and pH was 0.30. This solution was allowed to react by allowing it to stand for 3 days in a thermostatic bath at 50 ° C. The pH after the reaction was 0.23.
The obtained solution was centrifuged at 10,000 rpm for 10 minutes, the collected precipitate was washed with water, and a part thereof was observed with a transmission electron microscope (TEM) and magnified to 50,000 times and 100,000 times. Each particle photograph was taken (FIG. 3). From this photograph, the average maximum minor axis, average maximum major axis, aspect ratio, and coefficient of variation were measured by the above method. The average maximum minor axis was 15 nm, the average maximum major axis was 164 nm, the aspect ratio was 5.5, and the minor axis. The variation coefficient was 17%, and the variation coefficient of the major axis was 20%.
残りの沈殿を６０℃で乾燥させた後、粉砕し、図４に示すＸ線回折（ＸＲＤ）測定を行った。この結果、ルチル型酸化チタン粒子が得られたことが確認された。さらに、透過型電子顕微鏡観察時に電子線回折像を撮影し、得られたパターンがスポットパターンであったことから、該ルチル型粒子が単結晶粒子であることが確認された。 The remaining precipitate was dried at 60 ° C., pulverized, and X-ray diffraction (XRD) measurement shown in FIG. 4 was performed. As a result, it was confirmed that rutile type titanium oxide particles were obtained. Furthermore, an electron beam diffraction image was taken at the time of observation with a transmission electron microscope, and the obtained pattern was a spot pattern. Thus, it was confirmed that the rutile type particles were single crystal particles.
（実施例４）
１．６Ｍの過塩素酸（ＨＣｌＯ４）水溶液中に、同体積の０．５０Ｍのチタニウムイソプロポキシド（関東化学、以下「ＴＩＰＯ」と称す）水溶液を２５℃で添加し、攪拌して反応溶液を得た。得られた反応溶液における各成分の濃度（含有量）は、ＴＩＰＯ：０．２５Ｍ、ＨＣｌＯ４：０．８０Ｍ、ｐＨは０．３０であった。この溶液を、１０℃の恒温槽中で、３日間静置して反応させた。反応後のｐＨは、０．２３であった。
得られた溶液を、１０，０００回転で１０分間の遠心分離にかけ、回収できた沈殿を水洗し、６０℃で乾燥させた後、粉砕し、図４に示すＸ線回折（ＸＲＤ）測定を行った。この結果、ルチル型酸化チタン粒子が得られたことが確認された。さらに、透過型電子顕微鏡観察時に電子線回折像を撮影し、得られたパターンがスポットパターンであったことから、該ルチル型粒子が単結晶粒子であることが確認された。
Example 4
To a 1.6 M aqueous solution of perchloric acid (HClO 4 ), an equal volume of 0.50 M titanium isopropoxide (Kanto Chemical, hereinafter referred to as “TIPO”) is added at 25 ° C., and the reaction solution is stirred. Got. The concentration (content) of each component in the obtained reaction solution was TIPO: 0.25M, HClO 4 : 0.80M, and pH was 0.30. This solution was allowed to react for 3 days in a 10 ° C. constant temperature bath. The pH after the reaction was 0.23.
The obtained solution was centrifuged at 10,000 rpm for 10 minutes, and the recovered precipitate was washed with water, dried at 60 ° C., pulverized, and subjected to X-ray diffraction (XRD) measurement shown in FIG. It was. As a result, it was confirmed that rutile type titanium oxide particles were obtained. Furthermore, an electron beam diffraction image was taken at the time of observation with a transmission electron microscope, and the obtained pattern was a spot pattern. Thus, it was confirmed that the rutile type particles were single crystal particles.
（比較例１）
１４．９１９ｇのトリエタノールアミン（以下、「ＴＥＡ」と称す）中に、１４．２１ｇのＴＩＰＯを添加して攪拌した。攪拌を継続しながら、純水１００．００ｍｌをゆっくり滴下し、全量添加後に３０分攪拌させた（以下、「Ａ液」と称す）。このＡ液と２Ｍのアンモニア水を作製後、各２５ｍｌずつを攪拌混合して反応溶液を得た。得られた反応溶液における各成分の濃度（含有量）は、ＴＩＰＯ：０．２５Ｍ、ＴＥＡ：０．５０Ｍ、ＮＨ３：１Ｍ、ｐＨは１１．３０であった。耐圧性且つ耐熱性ガラス容器に全量を入れ、オーブン中に１００℃で２４時間投入した。得られたゼリー状物質を全てオートクレーブに入れ、１４０℃で３日間処理した。
これを、１０，０００回転で１０分間の遠心分離にかけ、回収できた沈殿を水洗し、一部を透過型電子顕微鏡（ＴＥＭ）観察し、５万倍及び１０万倍に拡大した粒子写真をそれぞれ撮影した（図５）。
残りの沈殿を６０℃で乾燥させた後、粉砕し、実施例１と同様にしてＸ線回折（ＸＲＤ）測定（図示せず）を行った結果、針状のアナターゼ型酸化チタン粒子が得られたことが確認された。
(Comparative Example 1)
14.21 g of TIPO was added to 14.919 g of triethanolamine (hereinafter referred to as “TEA”) and stirred. While continuing to stir, 100.00 ml of pure water was slowly added dropwise, and the whole amount was added and stirred for 30 minutes (hereinafter referred to as “solution A”). After preparing this A liquid and 2M ammonia water, 25 ml of each was stirred and mixed, and the reaction solution was obtained. The concentration (content) of each component in the obtained reaction solution was TIPO: 0.25M, TEA: 0.50M, NH 3 : 1M, and pH was 11.30. The whole amount was put into a pressure-resistant and heat-resistant glass container, and placed in an oven at 100 ° C. for 24 hours. The obtained jelly-like substance was all put in an autoclave and treated at 140 ° C. for 3 days.
This was centrifuged at 10,000 rpm for 10 minutes, the collected precipitate was washed with water, and a part of the photograph was observed with a transmission electron microscope (TEM). Photographed (FIG. 5).
The remaining precipitate was dried at 60 ° C., pulverized, and subjected to X-ray diffraction (XRD) measurement (not shown) in the same manner as in Example 1. As a result, acicular anatase-type titanium oxide particles were obtained. It was confirmed that
（比較例２）
Ｊ． Ｍａｔｅｒ． Ｃｈｅｍ．，２０００， Ｖｏｌ．１０， ２３８８−２３９１に記載のあるように、チタンイソプロポキシド（５ｍＬ）とイソプロパノール（５ｍＬ）を混合した溶液をｐＨ０．５の硝酸水溶液（４０ｍＬ）中に滴下し、８２℃・８時間の加熱でアルコール除去後、攪拌しながらオートクレーブ処理（２５０℃・２６時間）を行い、沈殿を得た。
この沈殿を十分洗浄後、走査型電子顕微鏡（ＳＥＭ）観察とＸ線回折（ＸＲＤ）測定（図示せず）を行った結果、球状のルチル型酸化チタン粒子が得られたことが確認された。
(Comparative Example 2)
J. et al. Mater. Chem. , 2000, Vol. 10, 2388-2391, a solution prepared by mixing titanium isopropoxide (5 mL) and isopropanol (5 mL) was dropped into an aqueous nitric acid solution (40 mL) at pH 0.5, and heated at 82 ° C. for 8 hours. After removing the alcohol, an autoclave treatment (250 ° C., 26 hours) was performed with stirring to obtain a precipitate.
After sufficiently washing the precipitate, scanning electron microscope (SEM) observation and X-ray diffraction (XRD) measurement (not shown) were carried out. As a result, it was confirmed that spherical rutile titanium oxide particles were obtained.
（比較例３）
特開平７−２５９８号公報の実施例２の方法、すなわち、以下の方法にて酸化チタンを生成した。
（１）ＴｉＯ2濃度２０７．９ｇ／Ｌの四塩化チタン水溶液（ＴｉＯ2重量基準で４６２．５ｇ相当量）を、５Ｌの四つ口フラスコに採取し、攪拌下７５℃に加温し、予め分散させたルチル型種晶スラリー（ＴｉＯ2重量基準で３７．５ｇ相当量）を添加し、７５℃で２時間加熱加水分解させ、ＴｉＯ2濃度１６３．２ｇ／Ｌのルチル結晶の二酸化チタンスラリー２９４１ｍＬを得た。
（２）前記（１）のスラリーを、５００ｍＬずつ１Ｌのビーカーに分取し、攪拌しながらＮａ2ＣＯ3粉末を添加して、スラリーｐＨ５まで中和後、それぞれにＴｉＯ2１００重量部に対し、Ｎａ4Ｐ2Ｏ7粉末を３０重量部添加して良く混合後、濾過、脱水したケーキを得た。該ケーキをそれぞれマッフル炉にて８７０℃で３時間焼成した。得られた焼成物は粉砕後、脱イオン水中に投入し、ミキサーで約１０分間混合後、濾過し、十分洗浄後、走査型電子顕微鏡（ＳＥＭ）観察とＸ線回折（ＸＲＤ）測定（図示せず）を行った結果、長径が１μｍ以上のルチル型酸化チタン粒子が得られたことが確認された。
(Comparative Example 3)
Titanium oxide was produced by the method of Example 2 of JP-A-7-2598, that is, the following method.
(1) A titanium tetrachloride aqueous solution having a TiO 2 concentration of 207.9 g / L (equivalent to 462.5 g based on the weight of TiO 2 ) is collected in a 5 L four-necked flask, heated to 75 ° C. with stirring, Dispersed rutile seed slurry (equivalent to 37.5 g based on TiO 2 weight) was added, hydrolyzed at 75 ° C. for 2 hours, and 2941 mL of rutile crystal titanium dioxide slurry having a TiO 2 concentration of 163.2 g / L. Got.
(2) The slurry of (1) above was dispensed into a 1 L beaker of 500 mL, and Na 2 CO 3 powder was added with stirring, neutralized to a slurry pH of 5, and then each 100 parts by weight of TiO 2. Then, 30 parts by weight of Na 4 P 2 O 7 powder was added and mixed well, and then a filtered and dehydrated cake was obtained. Each of the cakes was baked at 870 ° C. for 3 hours in a muffle furnace. The obtained fired product is pulverized, put into deionized water, mixed with a mixer for about 10 minutes, filtered, washed thoroughly, and observed with a scanning electron microscope (SEM) and X-ray diffraction (XRD) (not shown). As a result, it was confirmed that rutile-type titanium oxide particles having a major axis of 1 μm or more were obtained.
本発明のルチル型酸化チタン粒子は、正の複屈折性を有する酸化チタンの性質を利用して複屈折の調節が要請される用途（例えば、ＬＣＤやプロジェクタ用の位相差板、位相差フィルム）で好適に用いることができる。具体的には、光学用途において、例えば、偏向特性が重要で高精度が要求される光学素子を構成する樹脂に使用することができる。 The rutile-type titanium oxide particles of the present invention are used for applications in which birefringence adjustment is required using the properties of titanium oxide having positive birefringence (for example, retardation plates and retardation films for LCDs and projectors). Can be suitably used. Specifically, in an optical application, for example, it can be used as a resin constituting an optical element in which deflection characteristics are important and high accuracy is required.
Claims (2)
The method for producing rutile type titanium oxide according to claim 1, wherein rutile type titanium oxide particles which are single crystals are obtained .
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