JP5067824B2 - Titanium oxide powder - Google Patents
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- JP5067824B2 JP5067824B2 JP2004279122A JP2004279122A JP5067824B2 JP 5067824 B2 JP5067824 B2 JP 5067824B2 JP 2004279122 A JP2004279122 A JP 2004279122A JP 2004279122 A JP2004279122 A JP 2004279122A JP 5067824 B2 JP5067824 B2 JP 5067824B2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 159
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 115
- 239000000843 powder Substances 0.000 title claims description 89
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 41
- 239000007789 gas Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000012071 phase Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000003985 ceramic capacitor Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000012808 vapor phase Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 57
- 238000000034 method Methods 0.000 description 34
- 238000009826 distribution Methods 0.000 description 22
- 239000000463 material Substances 0.000 description 19
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 17
- 229910001882 dioxygen Inorganic materials 0.000 description 17
- 238000010574 gas phase reaction Methods 0.000 description 14
- 239000010408 film Substances 0.000 description 11
- 239000012535 impurity Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 8
- 229910002113 barium titanate Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000012776 electronic material Substances 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000112 cooling gas Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Description
本発明は比表面積が大きくかつルチル化率の高いルチル型の酸化チタン粉末に関し、具体的には、電子材料、紫外線遮蔽材料、光触媒材料、ディスプレイの反射防止膜、プラズマディスプレイなどの基盤用隔壁に用いるガラス材のフィラー材、または各種触媒の担体などに適した屈折率の高い酸化チタン粉末に関する。 The present invention relates to a rutile-type titanium oxide powder having a large specific surface area and a high rutile ratio, and specifically, for a partition wall for a substrate such as an electronic material, an ultraviolet shielding material, a photocatalyst material, an antireflection film for a display, and a plasma display. The present invention relates to a titanium oxide powder having a high refractive index suitable for a filler material of a glass material to be used or a carrier for various catalysts.
酸化チタン粉末は、白色顔料として古くから利用されており、近年は化粧品などの紫外線遮蔽材料、光触媒、コンデンサ、サーミスタの構成材料あるいはまたチタン酸バリウムの原料等電子材料に用いられる焼結材料に広く利用されている。また、酸化チタンは可視光付近の波長領域において大きな屈折率を示すため、可視光領域では殆ど光吸収は起こらない。このことから最近化粧料、医薬あるいは塗料等の紫外線遮蔽が要求されるような材料や、液晶ディスプレイ表示部やプラスティックレンズなどの反射防止膜として利用されている。反射防止膜は通常フッ素樹脂、シリコーン系樹脂などの低屈折率の樹脂などで形成される層と、高屈折率層を交互に重ねたものであり、酸化チタンはこの反射防止膜の高屈折率層の材料として用いられている。さらに最近需要の増えているプラズマディスプレイにおいては、その輝度を向上させるため、基盤用隔壁に用いられるガラス材に酸化チタンを被覆して反射率の改善を図ったり、ガラス材にルチル型酸化チタン粉末を配合して屈折率の改善を図ったりしている。 Titanium oxide powder has long been used as a white pigment, and in recent years, it has been widely used in sintered materials used for electronic materials such as UV shielding materials for cosmetics, photocatalysts, capacitors, thermistors, and barium titanate materials. It's being used. Further, since titanium oxide exhibits a large refractive index in the wavelength region near visible light, light absorption hardly occurs in the visible light region. For this reason, it has recently been used as an antireflective film for materials such as cosmetics, medicines, paints, and the like that require ultraviolet shielding, and for liquid crystal display portions and plastic lenses. The anti-reflective coating is a layer in which low-refractive-index resins such as fluororesin and silicone resin are usually layered alternately with a high-refractive index layer. Titanium oxide has a high refractive index. Used as layer material. Furthermore, in order to improve the brightness of plasma displays, which have recently been increasing in demand, the glass material used for the partition walls for the substrate is coated with titanium oxide to improve the reflectance, or the rutile titanium oxide powder is applied to the glass material. To improve the refractive index.
なお、ルチル型酸化チタンは、アナターゼ型酸化チタンに比べ、紫外線遮蔽効果や高屈折率などの光学的特性や高誘電特性などの電気特性において優れた性能を発揮することが知られている。 In addition, it is known that rutile type titanium oxide exhibits superior performance in electrical characteristics such as optical characteristics such as ultraviolet shielding effect and high refractive index and high dielectric characteristics, compared with anatase type titanium oxide.
酸化チタンの膜を形成するには、従来様々な方法が検討されている。例えば、基板表面に酸化チタンの薄膜を形成させる方法としては、蒸着法、ＣＶＤ法、スパッタ法などのドライ法、ゾル−ゲル法、メッキ法、電解重合法などのウェット法が知られている。しかしながらこれらの方法においてルチル型酸化チタン膜を形成するためには、酸化チタン膜を形成した後６００℃以上に加熱処理する必要があり、このため用いられる基材がガラス、セラミックスあるいは金属などの無機材料に限られ、その用途が限定されていた。そのためルチル型などの結晶性を持つ酸化チタン粉末をペーストなどの分散液とし、これを基材に塗布して膜を形成することも検討されている。しかしこのような酸化チタン粉末の塗布による方法において、膜の透明性を確保するために粒径をより小さくする必要がある。しかしながら従来の気相法や液相法を用いてより粒径の小さい酸化チタン粉末を製造しようとした場合、得られる酸化チタンの結晶型はルチル型にはならず、アモルファスあるいはアナターゼ型を相当量含むものであった。ルチル型に変換するためには更にこれらの酸化チタンを加熱処理することが必要であり、この加熱処理によって粒子の凝集が生じ、結果として微粒子を維持したままルチル型の酸化チタン粉末を得ることは困難であった。 Various methods have been studied for forming a titanium oxide film. For example, as a method for forming a thin film of titanium oxide on the substrate surface, dry methods such as vapor deposition, CVD, and sputtering, and wet methods such as sol-gel, plating, and electrolytic polymerization are known. However, in order to form a rutile-type titanium oxide film in these methods, it is necessary to heat-treat at 600 ° C. or higher after forming the titanium oxide film. For this reason, the substrate used is an inorganic material such as glass, ceramics or metal. It was limited to materials and its use was limited. For this reason, it has been studied to form a film by forming a rutile-type crystalline titanium oxide powder into a dispersion such as a paste and applying it to a substrate. However, in such a method by application of titanium oxide powder, it is necessary to make the particle size smaller in order to ensure the transparency of the film. However, when trying to produce titanium oxide powder with a smaller particle size using the conventional vapor phase method or liquid phase method, the crystal form of the resulting titanium oxide is not a rutile type, and a considerable amount of amorphous or anatase type is used. It was included. In order to convert to the rutile type, it is necessary to further heat-treat these titanium oxides. This heat-treatment causes the aggregation of particles, and as a result, it is possible to obtain rutile-type titanium oxide powder while maintaining the fine particles. It was difficult.
微粒子のルチル型酸化チタンを得る方法としては、特開平７−２９１６２９号公報に、超微粒子状アモルファス酸化チタンを、無機酸水溶液中で熟成させることにより超微粒子状ルチル型酸化チタンに変換する方法が開示されている。具体的には、有機チタン化合物や四塩化チタンから生成したアモルファス酸化チタンを塩酸水溶液や硫酸水溶液中で７２〜２４００時間熟成させた後、洗浄し乾燥させてルチル型酸化チタン微粒子を得るものである。
特開平７−２９１６２９号公報記載の方法によれば、得られた酸化チタン微粒子中にはルチル型結晶は含まれるものの、全体のルチル化率は必ずしも高くなく、より一層の改善が望まれていた。また、このような方法では、製造に長時間を要し、また工程も煩雑であり生産性が低く、実際に工業的には採用し難いという問題がある。 According to the method described in JP-A-7-291629, the obtained titanium oxide fine particles contain rutile crystals, but the overall rutile ratio is not necessarily high, and further improvement has been desired. . In addition, such a method has a problem that it takes a long time for production, the process is complicated, the productivity is low, and it is actually difficult to adopt industrially.
また、比表面積が比較的大きい微粒子の酸化チタン粉末は従来から知られているものの、これらの酸化チタン粉末はルチル型とアナターゼ型の混合物であって、比表面積が３０ｍ２／ｇ以上の場合にはルチル含有率（またはルチル化率）は約７０％以下であった。このように通常酸化チタン粉末はルチルとアナターゼの混合体であるため、粒度分布が比較的広いものであった。
一方、積層セラミックコンデンサの誘電体材料に用いられるチタン酸バリウムなどの原料に酸化チタン粉末が用いられる場合、誘電体粉末の粒径および粒度分布は、使用する酸化チタンの粒度また粒度分布に依存することが知られている。近年の小型化、高容量化のため、積層セラミックコンデンサの積層数は年々増加し、誘電体層および電極層は薄層化している。したがって、用いられる酸化チタン粉末は、より粒径が小さくかつ粒度分布の狭い粉末が要求されている。また、粉末の溶媒に対する分散性も重要であり、この点からも粒度分布の狭い粉末が要求されている。
Further, although fine titanium oxide powders having a relatively large specific surface area have been conventionally known, these titanium oxide powders are a mixture of a rutile type and an anatase type, and the specific surface area is 30 m 2 / g or more. The rutile content (or rutile ratio) was about 70% or less. Thus, since titanium oxide powder is usually a mixture of rutile and anatase, the particle size distribution was relatively wide.
On the other hand, when titanium oxide powder is used as a raw material such as barium titanate used for the dielectric material of the multilayer ceramic capacitor, the particle size and particle size distribution of the dielectric powder depend on the particle size and particle size distribution of the titanium oxide used. It is known. Due to the recent miniaturization and higher capacity, the number of laminated ceramic capacitors has increased year by year, and the dielectric layers and electrode layers have become thinner. Therefore, the titanium oxide powder used is required to have a smaller particle size and a narrow particle size distribution. In addition, the dispersibility of the powder in the solvent is also important, and from this point, a powder having a narrow particle size distribution is required.
従って、本発明の目的は、より粒径が小さくかつ粒度分布が狭く、高比表面積であり、かつルチル化率の高い酸化チタン粉末を提供することにある。 Accordingly, an object of the present invention is to provide a titanium oxide powder having a smaller particle size, a narrow particle size distribution, a high specific surface area, and a high rutile ratio.
本発明者は、上記従来技術に残された課題を解決すべく、鋭意研究を重ねた結果、より粒径が小さくかつ粒度分布が狭く、高比表面積であり、かつルチル化率の高い酸化チタン粉末を見出し、本発明を完成するに至った。 As a result of intensive studies to solve the problems remaining in the prior art, the present inventor has obtained a titanium oxide having a smaller particle size, a narrow particle size distribution, a high specific surface area, and a high rutile ratio. The powder was found and the present invention was completed.
すなわち、本発明の酸化チタン粉末は、四塩化チタンの気相反応により得られ、ルチル化率が８０％以上であって、ＢＥＴ比表面積が４３．０ｍ２／ｇ以上であることを特徴とするものである。 That is, the titanium oxide powder of the present invention is obtained by a gas phase reaction of titanium tetrachloride, and has a rutile ratio of 80% or more and a BET specific surface area of 43.0 m 2 / g or more. To do.
本発明の酸化チタン粉末は、従来のものとは異なり、ルチル化率が高いにも拘わらずＢＥＴ比表面積が大きく、チタン酸バリウムなどの電子材料、紫外線遮蔽材料、光触媒材料、反射防止膜や高反射率が要求されるプラズマディスプレイなどのガラス基材へのコート材やフィラー材として有効である。 Unlike the conventional ones, the titanium oxide powder of the present invention has a large BET specific surface area despite its high rutile ratio, and an electronic material such as barium titanate, an ultraviolet shielding material, a photocatalytic material, an antireflection film, and a high antireflection film. It is effective as a coating material or filler material for a glass substrate such as a plasma display that requires a reflectance.
本発明の酸化チタン粉末において、ルチル化率は８０％以上１００％以下、好ましくは８５％以上１００％以下、より好ましくは９０％以上１００％以下である。ルチル化率がこのような高い範囲であれば、例えば紫外線遮蔽効果や高屈折率などの光学的特性や高誘電特性などの電気特性において優れた性能を発揮する。 In the titanium oxide powder of the present invention, the rutile ratio is 80% or more and 100% or less, preferably 85% or more and 100% or less, and more preferably 90% or more and 100% or less. When the rutile ratio is in such a high range, excellent performance is exhibited in optical characteristics such as ultraviolet shielding effect and high refractive index, and electrical characteristics such as high dielectric characteristics.
ここで、ルチル化率の測定方法は、ＡＳＴＭ Ｄ３７２０−８４の方法に従いＸ線回折測定を行い、ルチル型結晶酸化チタンの最強回折線（面指数１１０）のピーク面積（Ｉｒ）と、アナターゼ型結晶酸化チタンの最強回折線（面指数１０１）のピーク面積（Ｉａ）を求め、次式により算出して求められる。 Here, the measurement method of the rutile ratio is X-ray diffraction measurement according to the method of ASTM D3720-84, the peak area (Ir) of the strongest diffraction line (surface index 110) of rutile-type crystalline titanium oxide, and the anatase-type crystal. The peak area (Ia) of the strongest diffraction line (surface index 101) of titanium oxide is obtained and calculated by the following formula.
ルチル化率（重量％）＝１００−１００／（１＋１．２×Ｉｒ／Ｉａ）
式中、ピーク面積（Ｉｒ）及びピーク面積（Ｉａ）は、Ｘ線回折スペクトルの該当回折線におけるベースラインから突出した部分の面積をいい、その算出方法は公知の方法で行えばよく、例えば、コンピュータ計算、近似三角形化などの手法により求められる。
Rutile ratio (% by weight) = 100-100 / (1 + 1.2 × Ir / Ia)
In the formula, the peak area (Ir) and the peak area (Ia) refer to the area of the portion protruding from the base line in the corresponding diffraction line of the X-ray diffraction spectrum, and the calculation method may be performed by a known method. It can be obtained by methods such as computer calculation and approximate triangulation.
また本発明の酸化チタン粉末において、ＢＥＴ比表面積は３０ｍ２／ｇ以上１００ｍ２／ｇ以下、好ましくは３３ｍ２／ｇ以上１００ｍ２／ｇ以下、より好ましくは３５ｍ２／ｇ以上１００ｍ２／ｇ以下である。ＢＥＴ比表面積が３０ｍ２／ｇ以上であれば、酸化チタン粉末の粒径が小さいものが得られる。 In the titanium oxide powder of the present invention, the BET specific surface area is 30 m 2 / g or more and 100 m 2 / g or less, preferably 33 m 2 / g or more and 100 m 2 / g or less, more preferably 35 m 2 / g or more and 100 m 2 / g or less. It is. When the BET specific surface area is 30 m 2 / g or more, a titanium oxide powder having a small particle size is obtained.
また当該酸化チタン粉末において、平均粒径は特に制限されないが、ＳＥＭ写真での画像解析による平均粒径で１００ｎｍ以下、好ましくは５〜７０ｎｍである。酸化チタン粉末の粒径がこのように小さければ、例えば積層セラミックコンデンサの積層数が増加し、誘電体層および電極層が薄層化しても対応できる。 Moreover, in the said titanium oxide powder, although an average particle diameter is not restrict | limited in particular, the average particle diameter by the image analysis in a SEM photograph is 100 nm or less, Preferably it is 5-70 nm. If the particle size of the titanium oxide powder is so small, for example, the number of laminated ceramic capacitors can be increased and the dielectric layer and the electrode layer can be made thinner.
さらに、本発明の酸化チタン粉末は不純物のきわめて少ない高純度であることが望ましく、酸化チタン粉末中に含まれるＦｅ、Ａｌ、ＳｉおよびＮａが各々１００ｐｐｍ未満でありかつＣｌが１０００ｐｐｍ未満である。望ましくはＦｅ、Ａｌ、ＳｉおよびＮａが各々２０ｐｐｍ未満であり、Ｃｌが５００ｐｐｍ未満、さらに望ましくは５０ｐｐｍ未満である。 Further, it is desirable that the titanium oxide powder of the present invention has a high purity with very few impurities, Fe, Al, Si and Na contained in the titanium oxide powder are each less than 100 ppm and Cl is less than 1000 ppm. Desirably, Fe, Al, Si and Na are each less than 20 ppm, and Cl is less than 500 ppm, more desirably less than 50 ppm.
以上のように本発明の酸化チタン粉末は、比表面積が大きく微粒子であるにもかかわらずルチル化率は非常に高く、さらに高純度であるので、チタン酸バリウムなどの電子材料用に用いた場合、誘電特性などの電気特性に優れるという利点を有する。 As described above, the titanium oxide powder of the present invention has a very high rutile ratio and a high purity in spite of a large specific surface area and fine particles, so that it is used for electronic materials such as barium titanate. In addition, it has an advantage of excellent electrical characteristics such as dielectric characteristics.
本発明の酸化チタン粉末を製造する方法としては、特に制限されないが、例えば、四塩化チタンを気相中で酸素と接触させ酸化させる気相酸化法、燃焼して水を生成する水素ガス等の可燃性ガスと酸素を燃焼バーナーに供給し火炎を形成し、この中に四塩化チタンを導入する火炎加水分解法などの気相法、および四塩化チタン、アルコキシチタンまたは硫酸チタニルなどを液相状態下で反応させて酸化チタンを得る液相法が挙げられる。これらの製法のなかでも、特に四塩化チタンを気相状態下で加水分解あるいは酸化反応させる気相法が本発明の高いルチル化率かつ高い比表面積を有する酸化チタン粉末を効率よく製造できる面で有利である。また、気相法は四塩化チタンを水素、酸素あるいは水蒸気と接触させ反応させるので、液相法で得られる酸化チタンのような不純物元素が混入また残留することがない。 The method for producing the titanium oxide powder of the present invention is not particularly limited. For example, a gas phase oxidation method in which titanium tetrachloride is oxidized by contacting oxygen in the gas phase, a hydrogen gas that burns to generate water, and the like. Combustible gas and oxygen are supplied to a combustion burner to form a flame, and a gas phase method such as a flame hydrolysis method in which titanium tetrachloride is introduced into this, and a liquid phase state such as titanium tetrachloride, alkoxytitanium or titanyl sulfate. There is a liquid phase method in which titanium oxide is obtained by reaction under the following conditions. Among these production methods, in particular, the gas phase method in which titanium tetrachloride is hydrolyzed or oxidized in a gas phase can efficiently produce titanium oxide powder having a high rutile ratio and a high specific surface area according to the present invention. It is advantageous. In the vapor phase method, titanium tetrachloride is brought into contact with hydrogen, oxygen, or water vapor and reacted, so that an impurity element such as titanium oxide obtained by the liquid phase method does not enter or remain.
以下、本発明の酸化チタン粉末を気相法において製造する方法について詳しく説明する。 Hereinafter, a method for producing the titanium oxide powder of the present invention in a gas phase method will be described in detail.
当該製造方法は、四塩化チタンを気相中で加水分解あるいは酸化させる方法であって、具体的には四塩化チタン蒸気を、水素ガス、酸素ガスおよび水蒸気を気相状態下で接触させ反応させる。このとき、四塩化チタンガスの反応部への供給量に対し、水蒸気の供給量を、四塩化チタンをすべて酸化する化学当量以上とすることをことが望ましい。水蒸気の供給量が、四塩化チタンをすべて酸化する化学当量未満であると、酸化チタンの生成反応が均一に行われないため、生成した酸化チタンの結晶制御ができず、高比表面積でルチル化率の高い酸化チタン粉末や、高比表面積でアナターゼ型の酸化チタン粉末を得ることは難しい。
ここで、四塩化チタンをすべて酸化する化学当量とは、四塩化チタンを水蒸気のみで反応させる場合の水蒸気の化学当量を意味し、つまり四塩化チタン１モルに対して水蒸気（水）を２モルである。本発明の方法において、水蒸気は四塩化チタンに対して過剰、具体的には供給ガスを標準状態としたときガスの容量で四塩化チタンガスの１０倍以上、好ましくは１００倍以上の水蒸気を供給し反応させる。また、酸素の供給量についても、四塩化チタンをすべて酸化する化学当量以上（四塩化チタン１モルに対して酸素１モル）が好ましく、具体的には供給ガスを標準状態としたときガスの容量で四塩化チタンガスの１０倍以上の酸素を供給し反応させる。
The production method is a method in which titanium tetrachloride is hydrolyzed or oxidized in a gas phase. Specifically, titanium tetrachloride vapor is reacted with hydrogen gas, oxygen gas and water vapor in contact with each other under the gas phase. . At this time, it is desirable that the supply amount of water vapor be equal to or more than the chemical equivalent for oxidizing all of titanium tetrachloride with respect to the supply amount of titanium tetrachloride gas to the reaction section. If the supply amount of water vapor is less than the chemical equivalent that oxidizes all titanium tetrachloride, the formation reaction of titanium oxide is not performed uniformly, so the crystal of the generated titanium oxide cannot be controlled, and the rutile is formed with a high specific surface area. It is difficult to obtain a titanium oxide powder having a high rate or an anatase type titanium oxide powder having a high specific surface area.
Here, the chemical equivalent that oxidizes all titanium tetrachloride means the chemical equivalent of water vapor when titanium tetrachloride is reacted only with water vapor, that is, 2 moles of water vapor (water) per mole of titanium tetrachloride. It is. In the method of the present invention, water vapor is excessive with respect to titanium tetrachloride. Specifically, when the supply gas is in a standard state, the gas volume is 10 times or more, preferably 100 times or more that of titanium tetrachloride gas. And react. Also, the supply amount of oxygen is preferably equal to or more than the chemical equivalent for oxidizing all of titanium tetrachloride (1 mol of oxygen with respect to 1 mol of titanium tetrachloride). Specifically, the gas volume when the supply gas is in a standard state In this step, oxygen is supplied at a rate 10 times or more that of titanium tetrachloride gas.
上記各成分の反応部への供給量比であるが、各供給ガスが標準状態としたとき四塩化チタン１ｌ（ガス）に対する水素ガス、酸素ガスおよび水蒸気の供給量は表１のとおりである。 Table 1 shows the supply ratio of hydrogen gas, oxygen gas, and water vapor to 1 l (gas) of titanium tetrachloride when each supply gas is in a standard state.
上記各原料ガスの供給量は、反応スケールあるいは各ガスを供給するノズル径等により異なるので適宜設定するが、反応部での各ガス、特に四塩化チタンガスの供給速度は乱流域になるように設定することが望ましい。また、供給する上記の各成分をアルゴンや窒素のごとき不活性ガスで希釈し反応部に供給し反応させることもできる。 The supply amount of each raw material gas varies depending on the reaction scale or the diameter of the nozzle that supplies each gas, etc., and is set as appropriate, but the supply rate of each gas, particularly titanium tetrachloride gas, in the reaction section is in a turbulent flow region. It is desirable to set. Further, each of the above components to be supplied can be diluted with an inert gas such as argon or nitrogen and supplied to the reaction section to be reacted.
また、上記の四塩化チタンガス、酸素ガス、水素ガス及び水蒸気を反応部に供給する際に、予め加熱して供給して反応させることが望ましく、具体的には７００〜１０００℃、好ましくは７５０〜９５０℃に加熱する。 Further, when supplying the titanium tetrachloride gas, oxygen gas, hydrogen gas and water vapor to the reaction part, it is desirable to heat and supply in advance to react, specifically 700 to 1000 ° C., preferably 750. Heat to ~ 950 ° C.
次いで反応させ酸化チタン粉末を生成させるが、このような酸化チタン粉末を気相反応で形成するためには、酸化チタンが生成する温度以上であり、好ましくは酸化チタンの結晶構造がルチル型に転移する温度より高い温度で反応を行う必要がある。具体的には、９００℃以下、好ましくは４００〜９００℃、特に好ましくは４５０〜８５０℃である。 Next, a titanium oxide powder is produced by reaction. In order to form such a titanium oxide powder by a gas phase reaction, the temperature is higher than the temperature at which titanium oxide is produced, and preferably the crystal structure of titanium oxide is transferred to the rutile type. It is necessary to carry out the reaction at a temperature higher than the temperature at which the reaction is performed. Specifically, it is 900 ° C. or less, preferably 400 to 900 ° C., particularly preferably 450 to 850 ° C.
上記のように各成分を反応させ酸化チタン粉末を生成させた後、生成粒子の凝集を防ぐために、少なくとも酸化チタン粒子が焼成する温度以下、具体的には３００℃未満まで可及的速やかに冷却を行う。 After producing the titanium oxide powder by reacting each component as described above, at least below the temperature at which the titanium oxide particles are baked, specifically, cooling to less than 300 ° C. as quickly as possible in order to prevent aggregation of the produced particles. I do.
上記のように得られた酸化チタン粉末は、その後粉末に含まれる塩化水素などの塩素分を加熱処理などにより除去し、必要に応じて分級あるいは篩分を行う。 From the titanium oxide powder obtained as described above, the chlorine content such as hydrogen chloride contained in the powder is then removed by heat treatment or the like, and classification or sieving is performed as necessary.
以下本発明の酸化チタン粉末を製造する具体的なプロセスの一例を示す。先ず、液状の四塩化チタンを予め８００〜９００℃に加熱し、気化させ、必要に応じて窒素ガスで希釈し反応炉に導入する。四塩化チタンの導入と同時に、予め８００〜９００℃加熱した酸素ガス、水素ガスおよび水蒸気を必要に応じて窒素ガスで希釈して反応炉に導入し、酸化反応を行うが反応温度は通常７００〜９００℃、好ましくは７５０〜９００℃である。本発明の酸化チタン粉末を得るためにはこのように比較的低温で酸化反応を行うことが望ましい。生成した酸化チタン粉末を冷却部に導入し、空気などの冷却ガスを酸化チタン粉末に接触させ、酸化チタン粉末を３００℃以下に冷却する。その後生成した酸化チタン粉末を捕集し、酸化チタン粉末中に残留する塩素分を、真空加熱、空気あるいは窒素ガス雰囲気中での加熱あるいはスチーム処理等の加熱処理あるいはアルコールとの接触処理により除去し、本発明の酸化チタン粉末を得ることができる。 An example of a specific process for producing the titanium oxide powder of the present invention is shown below. First, liquid titanium tetrachloride is preliminarily heated to 800 to 900 ° C., vaporized, diluted with nitrogen gas as necessary, and introduced into the reactor. Simultaneously with the introduction of titanium tetrachloride, oxygen gas, hydrogen gas and water vapor heated in advance at 800 to 900 ° C. are diluted with nitrogen gas as necessary and introduced into the reaction furnace to carry out the oxidation reaction, but the reaction temperature is usually 700 to 900 ° C, preferably 750 to 900 ° C. In order to obtain the titanium oxide powder of the present invention, it is desirable to carry out the oxidation reaction at a relatively low temperature as described above. The produced titanium oxide powder is introduced into the cooling section, a cooling gas such as air is brought into contact with the titanium oxide powder, and the titanium oxide powder is cooled to 300 ° C. or lower. Thereafter, the produced titanium oxide powder is collected, and the chlorine remaining in the titanium oxide powder is removed by vacuum heating, heating in air or nitrogen gas atmosphere, heating treatment such as steam treatment, or contact treatment with alcohol. The titanium oxide powder of the present invention can be obtained.
気相法による酸化チタン粉末の製造において、上記のような条件で製造することによって、酸化チタン粉末を無機酸水溶液中で熟成するなどのアナターゼ型酸化チタンをルチル化する工程を別途行わなくとも、本発明の高いルチル化率で高い比表面積を有する酸化チタン粉末を効率よく製造することができる。 In the production of titanium oxide powder by the vapor phase method, it is possible to produce the titanium oxide powder under the conditions as described above without performing a separate step of rutileizing the anatase-type titanium oxide such as aging the titanium oxide powder in an inorganic acid aqueous solution. The titanium oxide powder having a high specific surface area with a high rutile ratio according to the present invention can be produced efficiently.
本発明の酸化チタン粉末は、チタン酸バリウムなどの電子材料、紫外線遮蔽材料、反射防止膜や高反射率が要求されるプラズマディスプレイなどのガラス基材へのコート材やフィラー材として有効である。 The titanium oxide powder of the present invention is effective as a coating material or filler material for glass substrates such as electronic materials such as barium titanate, ultraviolet shielding materials, antireflection films and plasma displays that require high reflectivity.
次に、実施例を挙げて本発明を更に具体的に説明するが、これは単に例示であって本発明を制限するものではない。 EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, this is merely an example and does not limit the present invention.
（実施例１）
四塩化チタンを気相中で酸素ガス、水素ガスおよび水蒸気と接触させ酸化させる気相法により酸化チタン粉末を調製した。まず、多重管バーナーを上部に具備した内径４００ｍｍの気相反応管において、多重管バーナーに、８００℃に予熱し気化させた四塩化チタンガスを窒素ガスで希釈して供給し、一方別の供給ノズルより８００℃に予熱した水素ガス、酸素ガスおよび水蒸気を供給し、気相反応管内で８００℃にて酸化反応させ、酸化チタン粉末を生成させた。このとき四塩化チタンは標準状態として５００ｍｌ／分、酸素ガスは２０ｌ／分、水素ガスは２０ｌ／分、水蒸気は３７０l／分でそれぞれ供給した。その後、気相反応管の下部に位置する冷却部に室温の乾燥空気を８００ｌ／分で供給し、生成した酸化チタン粉末を冷却した。その後、得られた酸化チタン粉末を大気中で３５０℃〜４００℃で１０時間加熱処理した。このようにして得られた酸化チタン粉末について平均粒径、ルチル化率、比表面積、不純物の含量および粒度分布を測定し、その結果を表２に示した。なお、酸化チタン粉末の平均粒径、ルチル化率、比表面積、不純物の含量および粒度分布は以下の方法により測定した。
＜平均粒径＞
電子顕微鏡（ＳＥＭ）により粉末を観察し、インターセプト法により測定した。なお、解析数は２００個である。
＜ルチル化率＞
ＡＳＴＭ Ｄ ３７２０−８４に従いＸ線回折パターンにおける、ルチル型結晶酸化チタンの最強干渉線（面指数１１０）のピーク面積（Ｉｒ）と、酸化チタン粉末の最強干渉線（面指数１０１）のピーク面積（Ｉａ）を求め前述の算出式より求めた。なお、Ｘ線回折測定条件は下記の通りである。
Example 1
Titanium oxide powder was prepared by a vapor phase method in which titanium tetrachloride was oxidized in contact with oxygen gas, hydrogen gas and water vapor in the gas phase. First, in a gas phase reaction tube with an inner diameter of 400 mm equipped with a multi-tube burner, titanium tetrachloride gas preheated and vaporized to 800 ° C. is diluted with nitrogen gas and supplied to the multi-tube burner. Hydrogen gas, oxygen gas and water vapor preheated to 800 ° C. were supplied from a nozzle, and an oxidation reaction was carried out at 800 ° C. in a gas phase reaction tube to produce titanium oxide powder. At this time, titanium tetrachloride was supplied at a standard state of 500 ml / min, oxygen gas at 20 l / min, hydrogen gas at 20 l / min, and water vapor at 370 l / min. Thereafter, dry air at room temperature was supplied at 800 l / min to a cooling unit located in the lower part of the gas phase reaction tube, and the produced titanium oxide powder was cooled. Then, the obtained titanium oxide powder was heat-treated at 350 ° C. to 400 ° C. for 10 hours in the air. The average particle diameter, rutile ratio, specific surface area, impurity content and particle size distribution of the titanium oxide powder thus obtained were measured. The results are shown in Table 2. The average particle diameter, rutile ratio, specific surface area, impurity content and particle size distribution of the titanium oxide powder were measured by the following methods.
<Average particle size>
The powder was observed with an electron microscope (SEM) and measured by the intercept method. The number of analyzes is 200.
<Rutilization rate>
According to ASTM D 3720-84, the peak area (Ir) of the strongest interference line (surface index 110) of rutile crystalline titanium oxide and the peak area of the strongest interference line (surface index 101) of titanium oxide powder in the X-ray diffraction pattern ( Ia) was obtained and obtained from the above formula. The X-ray diffraction measurement conditions are as follows.
＜Ｘ線回折測定条件＞
・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・
回折装置 ＲＡＤ−１Ｃ（株式会社リガク製）
Ｘ線管球 Ｃｕ
管電圧・管電流 ４０ｋＶ、３０ｍＡ
スリット ＤＳ−ＳＳ：１度、ＲＳ：０．１５ｍｍ
モノクロメータ グラファイト
測定間隔 ０．００２度
計数方法 定時計数法
・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・
<X-ray diffraction measurement conditions>
・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・
Diffraction device RAD-1C (manufactured by Rigaku Corporation)
X-ray tube Cu
Tube voltage / tube current 40kV, 30mA
Slit DS-SS: 1 degree, RS: 0.15mm
Monochromator Graphite measurement interval 0.002 degree counting method Constant clock method ...
＜比表面積＞
ＢＥＴ法により測定した。
＜不純物の定量＞
酸化チタン中のＦｅ，Ａｌ，ＳｉおよびＮａ成分については原子吸光法により測定した。酸化チタン中のＣｌ成分については吸光光度法により測定した。
＜粒度分布＞
レーザー光散乱回折法粒度測定機（ＬＡ−７００：堀場製作所）を用い、適量の酸化チタン粉末を純水に懸濁させてから超音波をかけて３分間分散させ、粒度を測定し、体積統計値の粒度分布を求めた。なお、粒度分布は、Ｄ９０（積算粒度で９０％の粒径（μｍ））、Ｄ５０（積算粒度で５０％の粒径（μｍ））、Ｄ１０（積算粒度で１０％の粒径（μｍ））を求め、粒度分布（ＳＰＡＮ）を下記式で算出した。
ＳＰＡＮ＝（Ｄ９０−Ｄ１０）／Ｄ５０
<Specific surface area>
It was measured by the BET method.
<Quantitative determination of impurities>
The Fe, Al, Si and Na components in titanium oxide were measured by atomic absorption method. The Cl component in titanium oxide was measured by absorptiometry.
<Particle size distribution>
Using a laser light scattering diffraction particle size analyzer (LA-700: Horiba Seisakusho), suspend an appropriate amount of titanium oxide powder in pure water, then apply ultrasonic waves to disperse for 3 minutes, measure the particle size, and measure volume statistics. The particle size distribution of the values was determined. The particle size distributions are D90 (90% particle size (μm) in integrated particle size), D50 (50% particle size (μm) in integrated particle size), D10 (10% particle size (μm) in integrated particle size)). The particle size distribution (SPAN) was calculated by the following formula.
SPAN = (D90-D10) / D50
（参考例１）
四塩化チタンガス、水素ガス、酸素ガスおよび水蒸気予熱温度を８５０℃にした以外は実施例１と同様に酸化チタン粉末を製造した。得られた酸化チタン粒子の粒径、ルチル化率、比表面積、不純物の含量及び粒度分布を表２に示した。
( Reference Example 1 )
Titanium oxide powder was produced in the same manner as in Example 1 except that the titanium tetrachloride gas, hydrogen gas, oxygen gas, and steam preheating temperature were 850 ° C. Table 2 shows the particle diameter, rutile ratio, specific surface area, impurity content and particle size distribution of the obtained titanium oxide particles.
（参考例２）
四塩化チタンガス、水素ガス、酸素ガスおよび水蒸気予熱温度を９００℃にした以外は実施例１と同様に酸化チタン粉末を製造した。得られた酸化チタン粒子の粒径、ルチル化率、比表面積、不純物の含量及び粒度分布を表２に示した。
( Reference Example 2 )
Titanium oxide powder was produced in the same manner as in Example 1 except that the titanium tetrachloride gas, hydrogen gas, oxygen gas, and water vapor preheating temperature were set to 900 ° C. Table 2 shows the particle diameter, rutile ratio, specific surface area, impurity content and particle size distribution of the obtained titanium oxide particles.
（参考例３）
水素ガスおよび酸素ガスの供給量をそれぞれ４０ｌ／分にした以外は実施例１と同様に酸化チタン粉末を製造した。得られた酸化チタン粒子の粒径、ルチル化率、比表面積、不純物の含量及び粒度分布を表２に示した。
( Reference Example 3 )
Titanium oxide powder was produced in the same manner as in Example 1 except that the supply amounts of hydrogen gas and oxygen gas were 40 l / min. Table 2 shows the particle diameter, rutile ratio, specific surface area, impurity content and particle size distribution of the obtained titanium oxide particles.
（比較例１）
まず、多重管バーナーを上部に具備した内径４００ｍｍの気相反応管において、多重管バーナーに、１１００℃に予熱し気化させた四塩化チタンガスを窒素ガスで希釈して供給し、一方別の供給ノズルより１０００℃に予熱した酸素ガスと水蒸気の混合ガスを供給し、気相反応管内で１０００℃にて酸化反応させ、酸化チタン粉末を生成させた。このとき四塩化チタンは標準状態として５００ｍｌ／分、酸素ガスは３４０ｍｌ／分、水蒸気は８５０ｍｌ／分でそれぞれ供給した。その後、気相反応管の下部に位置する冷却部に室温の乾燥空気を８００ｌ／分で供給し、生成した酸化チタン粉末を冷却した。このようにして得られた酸化チタン粉末について平均粒径、ルチル化率、比表面積、不純物の含量及び粒度分布を測定し、その結果を表２に示した。
(Comparative Example 1)
First, in a gas phase reaction tube having an inner diameter of 400 mm equipped with a multi-tube burner, titanium tetrachloride gas preheated to 1100 ° C. and vaporized is supplied to the multi-tube burner after being diluted with nitrogen gas, and supplied separately. A mixed gas of oxygen gas and water vapor preheated to 1000 ° C. was supplied from a nozzle and subjected to an oxidation reaction at 1000 ° C. in a gas phase reaction tube to produce titanium oxide powder. At this time, titanium tetrachloride was supplied at a standard state of 500 ml / min, oxygen gas at 340 ml / min, and water vapor at 850 ml / min. Thereafter, dry air at room temperature was supplied at 800 l / min to a cooling unit located in the lower part of the gas phase reaction tube, and the produced titanium oxide powder was cooled. The average particle diameter, rutile ratio, specific surface area, impurity content and particle size distribution of the titanium oxide powder thus obtained were measured. The results are shown in Table 2.
（比較例２）
まず、多重管バーナーを上部に具備した内径４００ｍｍの気相反応管において、多重管バーナーに、８００℃に予熱し気化させた四塩化チタン及び水素ガスの混合ガスを供給し、一方別の供給ノズルより８００℃に予熱した酸素ガスを供給し、気相反応管内で約１０００℃にて酸化反応させ、酸化チタン粉末を生成させた。このとき四塩化チタンは６０ｌ／分、水素ガスは４０ｌ／分、酸素ガスは３８０ｌ／分でそれぞれ供給した。その後、気相反応管の底部から空気を４００ｌ／分で挿入し、生成した酸化チタン粉末を冷却した。その後、得られた酸化チタン粉末を大気中で３５０℃〜４００℃で１０時間加熱処理した。このようにして得られた酸化チタン粉末について粒径、ルチル化率、比表面積、不純物の含量および粒度分布を測定し、その結果を表２に示した。
(Comparative Example 2)
First, in a gas phase reaction tube having an inner diameter of 400 mm equipped with a multi-tube burner, a mixed gas of titanium tetrachloride and hydrogen gas preheated and vaporized to 800 ° C. is supplied to the multi-tube burner. Further, oxygen gas preheated to 800 ° C. was supplied and oxidized at about 1000 ° C. in a gas phase reaction tube to produce titanium oxide powder. At this time, titanium tetrachloride was supplied at 60 l / min, hydrogen gas at 40 l / min, and oxygen gas at 380 l / min. Thereafter, air was inserted from the bottom of the gas phase reaction tube at 400 l / min, and the produced titanium oxide powder was cooled. Then, the obtained titanium oxide powder was heat-treated at 350 ° C. to 400 ° C. for 10 hours in the air. The titanium oxide powder thus obtained was measured for particle size, rutile ratio, specific surface area, impurity content, and particle size distribution, and the results are shown in Table 2.
（比較例３）
まず、多重管バーナーを上部に具備した内径４００ｍｍの気相反応管において、多重管バーナーに、約８００℃に予熱し気化させた四塩化チタンガスを供給し、一方別の供給ノズルより８００℃に予熱した酸素ガス及び水蒸気を供給し、気相反応管内で約１０００℃にて酸化反応させ、酸化チタン粉末を生成させた。このとき四塩化チタンは２００ｌ／分、酸素ガスは３８０ｌ／分、水蒸気は１７０ｌ／分でそれぞれ供給した。その後、気相反応管の底部から空気を１００ｌ／分で挿入し、生成した酸化チタン粉末を冷却した。その後、得られた酸化チタン粉末を大気中で３５０℃〜４００℃で１０時間加熱処理した。このようにして得られた酸化チタン粉末について粒径、ルチル化率、比表面積、不純物の含量および粒度分布を測定し、その結果を表２に示した。
(Comparative Example 3)
First, in a gas phase reaction tube having an inner diameter of 400 mm equipped with a multi-tube burner, titanium tetrachloride gas preheated and vaporized to about 800 ° C. is supplied to the multi-tube burner, and at 800 ° C. from another supply nozzle. Preheated oxygen gas and water vapor were supplied, and an oxidation reaction was performed at about 1000 ° C. in a gas phase reaction tube to produce titanium oxide powder. At this time, titanium tetrachloride was supplied at 200 l / min, oxygen gas at 380 l / min, and water vapor at 170 l / min. Thereafter, air was inserted at 100 l / min from the bottom of the gas phase reaction tube, and the produced titanium oxide powder was cooled. Then, the obtained titanium oxide powder was heat-treated at 350 ° C. to 400 ° C. for 10 hours in the air. The titanium oxide powder thus obtained was measured for particle size, rutile ratio, specific surface area, impurity content, and particle size distribution, and the results are shown in Table 2.
表２から明らかなように、実施例１及び参考例１〜３はいずれも、酸素ガスおよび水素ガスは四塩化チタンに対して少量であり、水蒸気は四塩化チタンに対して過剰に供給し８００〜９００℃で反応させるため、得られた酸化チタン粉末のルチル化率は８９．５％以上と高くかつ比表面積３４ｍ２／ｇ以上と高かった。また、平均粒径は５０ｎｍ以下と非常に微粒子にも拘わらず、狭い粒度分布を有しており、同時に溶媒中での分散性にも優れている。比較例１および３は、水素ガスの供給がなく、水蒸気量が過剰には供給されないため、比表面積は３０ｍ２／ｇ未満となり、粒度分布も広いものであった。また、比較例２は、水蒸気の供給がないため、比表面積が小さく、また粒度分布も広いものであった。 As is clear from Table 2, in Example 1 and Reference Examples 1 to 3 , oxygen gas and hydrogen gas were a small amount relative to titanium tetrachloride, and water vapor was supplied in excess relative to titanium tetrachloride. Since the reaction was performed at ˜900 ° C., the rutile ratio of the obtained titanium oxide powder was as high as 89.5% or more and as high as 34 m 2 / g or more in specific surface area. In addition, although the average particle size is very small as 50 nm or less, it has a narrow particle size distribution and at the same time has excellent dispersibility in a solvent. In Comparative Examples 1 and 3, since hydrogen gas was not supplied and the amount of water vapor was not supplied excessively, the specific surface area was less than 30 m 2 / g and the particle size distribution was wide. In Comparative Example 2, there was no supply of water vapor, so the specific surface area was small and the particle size distribution was wide.
（実施例２、参考例４〜６及び比較例４〜６）
実施例１、参考例１〜３および比較例１〜３で得られた酸化チタンと、炭酸バリウムを同モルづつ混合し、ボールミルで湿式粉砕した。次いで、濾過、乾燥した後、室温から１１４０℃まで昇温速度１８０℃／時間で加熱し、１１４０℃で２時間焼成し、チタン酸バリウム粉末を得た。得られたチタン酸バリウム粉末１００モルに対し、酸化バリウム０．５８モル、酸化カルシウム０．４２モル、酸化マグネシウム２.００モル、酸化マンガン０．３７５モル、酸化珪素３．００モル、酸化ディスプロシウム２．１３モル、酸化バナジウム０．０５０モル、酸化タンタル０．５００モルのモル数で秤量し、これらの粉末をボールミルを用いて１６時間湿式混合粉砕し、誘電体組成物を作製した。得られた各誘電体組成物粉末に、分散剤とバインダーとしてＰＶＢを加え、更に分散媒としてセロソルブ系の有機溶剤を加え、ビーズミルにてスラリーを作製した。次いで、このスラリーをドクターブレード法にて製膜し、膜厚２０μｍのグリーンシートを作製した。このグリーンシートに、ニッケル粉ペーストを所定の印刷パターンで印刷し、内部電極とした。内部電極が印刷されたグリーンシートを、所定枚数トリミング積層し、その後、熱プレスすることでグリーン積層体を得た。このグリーン積層体を、大気雰囲気中３５０℃で脱バインダーの後、加湿された水素と窒素の混合ガスの中で、１３００℃で２時間焼成し、次いで、１０００℃で６時間、窒素雰囲気中でアニールした。この焼成体に、外部電極として銅ペーストを焼き付けて積層セラミックコンデンサを得た。得られた各積層セラミックコンデンサについて、ＬＣＲメーター（１ｋＨ、１Ｖ）により誘電率を測定した。結果を表３に示す。
(Example 2, Reference Examples 4 to 6 and Comparative Examples 4 to 6)
The titanium oxide obtained in Example 1 , Reference Examples 1 to 3 and Comparative Examples 1 to 3 and barium carbonate were mixed in the same mole and wet pulverized with a ball mill. Subsequently, after filtering and drying, it heated from room temperature to 1140 degreeC with the temperature increase rate of 180 degreeC / hour, and baked at 1140 degreeC for 2 hours, and obtained the barium titanate powder. With respect to 100 mol of the obtained barium titanate powder, 0.58 mol of barium oxide, 0.42 mol of calcium oxide, 2.00 mol of magnesium oxide, 0.375 mol of manganese oxide, 3.00 mol of silicon oxide, oxidized dyspro A dielectric composition was prepared by weighing 2.13 mol of calcium, 0.050 mol of vanadium oxide and 0.500 mol of tantalum oxide, and wet-grinding these powders for 16 hours using a ball mill. To each of the obtained dielectric composition powders, PVB was added as a dispersant and a binder, a cellosolve organic solvent was added as a dispersion medium, and a slurry was prepared with a bead mill. Subsequently, this slurry was formed into a film by a doctor blade method to produce a green sheet having a thickness of 20 μm. On this green sheet, a nickel powder paste was printed with a predetermined printing pattern to form internal electrodes. A predetermined number of green sheets printed with internal electrodes were trimmed and laminated, and then hot pressed to obtain a green laminate. This green laminate was debindered at 350 ° C. in an air atmosphere, then fired in a humidified mixed gas of hydrogen and nitrogen at 1300 ° C. for 2 hours, and then at 1000 ° C. for 6 hours in a nitrogen atmosphere. Annealed. The fired body was baked with copper paste as an external electrode to obtain a multilayer ceramic capacitor. About each obtained multilayer ceramic capacitor, the dielectric constant was measured with the LCR meter (1 kHz, 1V). The results are shown in Table 3.
表３から明らかなように、実施例２及び参考例４〜６の積層セラミックコンデンサは、本発明のルチル化率８０％以上、ＢＥＴ比表面積３０ｍ２／ｇ以上の酸化チタン粉末（実施例１及び参考例１〜３）を使用して製造されたチタン酸バリウムを主原料として作製された積層セラミックコンデンサであり、比較例４〜６に比べて誘電率が高く、誘電特性に優れるものであった。 As can be seen from Table 3, the multilayer ceramic capacitors of Example 2 and Reference Examples 4 to 6 are titanium oxide powders (Examples 1 and 4) of the present invention having a rutile ratio of 80% or more and a BET specific surface area of 30 m 2 / g or more. It is a multilayer ceramic capacitor produced using barium titanate produced by using Reference Examples 1 to 3 ) as a main raw material, and has a higher dielectric constant and excellent dielectric properties than Comparative Examples 4 to 6. .
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