JPH0446016A - Production of colored titanium oxide - Google Patents
Production of colored titanium oxideInfo
- Publication number
- JPH0446016A JPH0446016A JP15226490A JP15226490A JPH0446016A JP H0446016 A JPH0446016 A JP H0446016A JP 15226490 A JP15226490 A JP 15226490A JP 15226490 A JP15226490 A JP 15226490A JP H0446016 A JPH0446016 A JP H0446016A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- gas
- colored titanium
- reaction
- colored
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 58
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000010936 titanium Substances 0.000 claims abstract description 21
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- -1 titanium alkoxide Chemical class 0.000 claims abstract description 13
- 238000006722 reduction reaction Methods 0.000 claims abstract description 7
- 238000005507 spraying Methods 0.000 claims abstract 2
- 239000010419 fine particle Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 41
- 239000002245 particle Substances 0.000 abstract description 22
- 239000007789 gas Substances 0.000 abstract description 11
- 239000012159 carrier gas Substances 0.000 abstract description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- 230000002829 reductive effect Effects 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000012495 reaction gas Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229940057995 liquid paraffin Drugs 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000002076 thermal analysis method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910009848 Ti4O7 Inorganic materials 0.000 description 1
- 229910010280 TiOH Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野］
有色酸化チタンは、カーボンブランクや酸化鉄（マグネ
タイト）等と同様に黒色顔料として使用される。また、
最近は、新素材としての種々な特性が明らかにされ、そ
の特性を利用するさまざまな機能、用途の開発が期待さ
れている。[Detailed Description of the Invention] [Industrial Application Field] Colored titanium oxide is used as a black pigment like carbon blank, iron oxide (magnetite), and the like. Also,
Recently, various properties of new materials have been revealed, and there are expectations for the development of various functions and applications that utilize these properties.
この発明は、このような有色チタンの製造方法に関する
ものである。The present invention relates to a method for manufacturing such colored titanium.
［従来の技術］
有色酸化チタンの製造方法としては、二酸化チタンと金
属チタン粉末との混合粉末を真空中で焼結するもの（特
公昭５２−１２７３３号）や、二酸化チタンを水素ガス
中で加熱還元する方法を改良し、アンモニアガス中で加
熱還元するようにしたもの（特公昭６４−２５６７号）
などが提案されている。[Prior art] Methods for producing colored titanium oxide include sintering a mixed powder of titanium dioxide and metallic titanium powder in a vacuum (Japanese Patent Publication No. 12733/1982), and heating titanium dioxide in hydrogen gas. An improved method of reducing by heating and reducing in ammonia gas (Special Publication No. 2567/1983)
etc. have been proposed.
〔発明が解決しようとする課題）
しかし、混合粉末を真空中で焼結するものは、個相−固
相聞で酸化還元反応を起こすために、生成物が焼結や粒
成長して粒子径が大きくなる傾向がある。一方、二酸化
チタンをアンモニアガス中で加熱還元するものは、水素
ガスの場合だと反応温度が１２００°Ｃ−１６００°Ｃ
で生成物の焼結や粒成長が起こりやすいのに対し、５０
０’Ｃ−１０００゛Ｃという低い温度で反応が行われる
ため、生酸物の焼結や粒成長の問題は改善されるが、バ
ンチ弐であるため、量産が困難であり、反応時間も８時
間という長時間を必要とする。[Problem to be solved by the invention] However, when mixed powder is sintered in vacuum, an oxidation-reduction reaction occurs between the solid phase and the product, resulting in sintering and grain growth, resulting in a decrease in particle size. tends to become larger. On the other hand, when titanium dioxide is heated and reduced in ammonia gas, the reaction temperature is 1200°C-1600°C in the case of hydrogen gas.
While sintering and grain growth of the product is likely to occur at 50
Since the reaction is carried out at a low temperature of 0'C to 1000°C, the problems of sintering and grain growth of the raw oxide are improved, but mass production is difficult because it is done in bunches, and the reaction time is 8 It requires a long time.
また、何れも原料の二酸化チタンの粒子径により生成酸
化チタンの粒子径が影響される。従って顔料として使用
するには、粉砕工程が必要である。Furthermore, in both cases, the particle size of the produced titanium oxide is influenced by the particle size of the raw material titanium dioxide. Therefore, a pulverization step is necessary for use as a pigment.
この発明は、有色酸化チタンの製造方法における上記問
題を解決するものであって、粒子径が極めて小さく、粉
砕工程が不要な有色酸化チタンを連続的に生成すること
ができ生産性のよい、有色酸化チタンの製造方法を提供
することを目的とする。This invention solves the above-mentioned problems in the method for producing colored titanium oxide, and is capable of continuously producing colored titanium oxide with an extremely small particle size and no pulverization process, and with high productivity. The object of the present invention is to provide a method for producing titanium oxide.
（課題を解決するための手段〕
上記課題を解決するため、この発明の有色酸化チタンの
製造方法では、チタンアルコキシドを還元ガス雰囲気中
へ、超音波噴霧器やガラス製超微細噴霧器等を用いて噴
霧供給して、分解還元反応を行なうことにより有色酸化
チタンの微粒子を連続的に生成させる。チタンアルコキ
シドの分解は、８００ ”Ｃ以上の温度で行なうことが
望ましい。(Means for Solving the Problems) In order to solve the above problems, in the method for producing colored titanium oxide of the present invention, titanium alkoxide is sprayed into a reducing gas atmosphere using an ultrasonic atomizer, a glass ultrafine atomizer, etc. The titanium alkoxide is supplied and a decomposition-reduction reaction is carried out to continuously produce colored titanium oxide fine particles.Titanium alkoxide is preferably decomposed at a temperature of 800''C or higher.
チタンアルコキシドが水素やアンモニアなどの還元ガス
雰囲気中へ噴霧供給されると、分解還元反応が行なわれ
、有色酸化チタンの微粒子が連続的に生成される。When titanium alkoxide is sprayed into an atmosphere of a reducing gas such as hydrogen or ammonia, a decomposition-reduction reaction takes place and colored titanium oxide fine particles are continuously produced.
生成される有色酸化チタンは、粒子径が１μｍ以下であ
り、還元ガスが水素の場合にはＴｉｎ０□１−４、（Ｔ
１ ：＋ Ｏ＝、 、Ｔ １ ａ ０７等）とＴｉＯ
２とで構成され、反応温度によって生成物の色彩がグレ
ー（８００°Ｃ以下）から水色さらに青黒色（１２００
°Ｃ）へと変化する。還元ガスがアンモニアの場合には
、Ｔｉ０ｈから窒素がドープしたＴｉＯへと反応が進行
し、Ｏ／Ｔｉの比がより１に近づき、色彩が反応温度に
よって、灰緑色から紫黒色へ変化する。The produced colored titanium oxide has a particle size of 1 μm or less, and when the reducing gas is hydrogen, it is Tin0□1-4, (T
1:+O=, , T 1 a 07, etc.) and TiO
The color of the product varies from gray (below 800°C) to light blue to blue-black (below 1200°C) depending on the reaction temperature.
°C). When the reducing gas is ammonia, the reaction progresses from TiOH to nitrogen-doped TiO, the O/Ti ratio approaches 1, and the color changes from gray-green to purple-black depending on the reaction temperature.
これらの有色酸化チタンは、３００°Ｃ〜から４００℃
付近まで熱的に安定であり、すぐれた分散性を示す。These colored titanium oxides can be heated from 300°C to 400°C.
It is thermally stable up to approximately
〔実施例］
第１図に示す装置を用いて、有色酸化チタンの製造を行
った。図において、ｌは、原料のチタンアルコキシドを
供給する微量定量ポンプ、２は微量定量ポンプから供給
された原料を微細化し噴霧する微細噴霧装置、３はキャ
リアガス導入口、４は分解還元反応を行なう石英ガラス
製の反応−管、５は反応管４で生成された有色酸化チタ
ンを補集する捕集装置、６はガス吸収トランプ、７は反
応ガスを反応管４へ供給する反応ガス導入口、８は反応
管４を加熱し反応温度を制御する電気炉、９は捕集装置
５で補集された有色酸化チタンを系外へ取り比す連続取
出装置である。[Example] Colored titanium oxide was produced using the apparatus shown in FIG. In the figure, l is a micro-metering pump that supplies titanium alkoxide as a raw material, 2 is a fine spray device that atomizes and sprays the raw material supplied from the micro-metering pump, 3 is a carrier gas inlet, and 4 is a decomposition-reduction reaction. A reaction tube made of quartz glass, 5 a collection device for collecting colored titanium oxide produced in the reaction tube 4, 6 a gas absorption lamp, 7 a reaction gas inlet for supplying reaction gas to the reaction tube 4, 8 is an electric furnace that heats the reaction tube 4 and controls the reaction temperature, and 9 is a continuous extraction device that takes the colored titanium oxide collected by the collection device 5 out of the system.
（実施例１）
原料のチタンアルコキシドとして、チタンテトライソプ
ロポキサイド（以下ＴＴ Ｉ Ｐという）２０ ｇ／ｈ
を微量定量ポンプ１で微細噴霧装置２へ定量供給し、窒
素ガス５１ノａｉｎをキャリアガスとして反応管４内へ
噴霧供給し−た。反応管４内は、水素ガス５ ｆ／ｓｉ
ｎを反応ガスとして反応ガス導入ロアから供給し還元ガ
ス雰囲気とした。この反応管４を電気炉８で所定温度に
加熱して反応管４内に供給された、ＴＴＩＰを熱分解し
、水素による還元反応で有色酸化チタンを生成させた。(Example 1) As a raw material titanium alkoxide, titanium tetraisopropoxide (hereinafter referred to as TT I P) 20 g/h
was supplied in a fixed amount to a fine spray device 2 using a micrometer metering pump 1, and 51 noa of nitrogen gas was sprayed into a reaction tube 4 as a carrier gas. Inside the reaction tube 4, hydrogen gas 5 f/si
n was supplied as a reaction gas from the reaction gas introduction lower to create a reducing gas atmosphere. This reaction tube 4 was heated to a predetermined temperature in an electric furnace 8 to thermally decompose the TTIP supplied into the reaction tube 4, and colored titanium oxide was produced by a reduction reaction with hydrogen.
この生成された有色酸化チタンは捕集装置５で捕集し、
連続取出装置９から随時系外へ取出した。This generated colored titanium oxide is collected by a collection device 5,
It was taken out of the system from the continuous extraction device 9 at any time.
第２図は、得られた有色酸化チタンのＸ線回折（照射：
Ｃｕ−Ｋａ波長１．５４１８人）の結果を示している。Figure 2 shows the X-ray diffraction (irradiation:
The results are shown for Cu-Ka wavelength 1.5418 people).
この図から反応温度８００°Ｃでは、ＴｉＯ□ （アナ
ターゼ形、僅かにルチル形）、反応温度１０００″Ｃで
はＴ：０２ （アナターゼ形及びルチル形）、反応温度
１２００゛ＣではＴｉｎＯ７及びＴｉ、○、が得られて
おり、反応温度が高くなるに従って低次酸化チタン（酸
素とＴｉの比がより１に近い）となることがわかる。From this figure, at a reaction temperature of 800°C, TiO□ (anatase form, slightly rutile form), at a reaction temperature of 1000"C, T:02 (anatase form and rutile form), and at a reaction temperature of 1200°C, TinO7 and Ti, ○ It can be seen that the higher the reaction temperature, the lower the titanium oxide (the ratio of oxygen to Ti is closer to 1).
第１表
第１表には、得られた有色酸化チタンの色調をＪＩＳＺ
−８７２９により測定した結果をＬ’ｓ ａ ＊ｂ“表
示系で示している。反応温度が高くなるに従って明度が
小さくなり、黒くなる傾向を示し、灰色から水色さらに
青黒色へと変化することがわかる。Table 1 Table 1 shows the color tone of the obtained colored titanium oxide according to JISZ
-8729 is shown in the L'sa*b" display system. As the reaction temperature increases, the brightness decreases and tends to become black, and the color may change from gray to light blue to blue-black. Recognize.
第３図は、反応温度１２００″Ｃで得られた有色酸化チ
タン粒子の電子顕微鏡によるＴＥＭ （透過像）を示す
。この電子顕微鏡による観察の結果から、平均粒子径が
０．１〜０．５μＭと極めて小さく、鎖状であることが
わかる。Figure 3 shows a TEM (transmission image) taken by an electron microscope of colored titanium oxide particles obtained at a reaction temperature of 1200''C. From the results of observation with this electron microscope, the average particle diameter was 0.1 to 0.5 μM. It can be seen that it is extremely small and chain-like.
第４図は、反応温度１２００ ’Ｃで得られた有色酸化
チタン粒子の加熱による熱的挙動、重量変化量をｆ＋！
認するために行った熱分析の結果を示している。有色チ
タンは３１６°Ｃと４１６°Ｃに発熱ピークを示し、か
なり高温まで熱的に安定であること、３００ ’Ｃ付近
から僅かに重量が増加することが認められた。Figure 4 shows the thermal behavior and weight change due to heating of colored titanium oxide particles obtained at a reaction temperature of 1200'C.
The figure shows the results of thermal analysis conducted to confirm the Colored titanium showed exothermic peaks at 316°C and 416°C, was found to be thermally stable up to considerably high temperatures, and slightly increased in weight from around 300'C.
第５図は、反応温度１２００°Ｃで得られた有色酸化チ
タン粒子の赤外吸収スペクトルを示す。この結果から炭
化水素は発生していないものと考えられる。FIG. 5 shows an infrared absorption spectrum of colored titanium oxide particles obtained at a reaction temperature of 1200°C. From this result, it is considered that no hydrocarbons were generated.
第６図はこの実施例のキャリヤガスを窒素ガスに代えて
水素ガスとした場合のＸ線回折結果を示している。還元
力を高めたため、より低次のを色酸化チタンＴｉｅ、及
びＴｉ４Ｏ７が生成された。FIG. 6 shows the results of X-ray diffraction when hydrogen gas was used instead of nitrogen gas as the carrier gas in this example. Since the reducing power was increased, lower colored titanium oxide Tie and Ti4O7 were produced.
（実施例２）
原料のチタンアルコキシドとしてＴＴＩＰ１８ｇ／ｈを
微細噴霧装置２へ供給し、窒素ガス５ｊ２／ｍｉｎをキ
ャリアガスとして反応管４内へ噴霧供給した。反応管４
内には、アンモニアガス２β／ｍｉｎを反応ガスとして
供給し、実施例１と同様にして、有色酸化チタンを生成
させた。(Example 2) 18 g/h of TTIP was supplied as a raw material titanium alkoxide to the fine spray device 2, and 5j2/min of nitrogen gas was sprayed into the reaction tube 4 as a carrier gas. Reaction tube 4
Ammonia gas was supplied at 2β/min as a reaction gas, and colored titanium oxide was produced in the same manner as in Example 1.
第７図は、得られた有色酸化チタンのＸ線回折の結果を
示している。反応温度８００°ＣではＴｉＯ２（アナタ
ーゼ形）、反応温度ｉｏｏ、ｏ°ＣではＴｉ０ｚ（僅か
にルチル形が混入したアナターゼ形）、反応温度１２０
０ ”ＣではＴｉＯが得られた。このＴｉＯは熱処理を
行なうことにより、容易にＴｉＮとなる。第８図はその
Ｘ線回折の結果を示している。FIG. 7 shows the results of X-ray diffraction of the obtained colored titanium oxide. TiO2 (anatase form) at reaction temperature 800°C, Ti0z (anatase form slightly mixed with rutile form) at reaction temperature ioo and o°C, reaction temperature 120°C.
At 0''C, TiO was obtained. This TiO easily becomes TiN by heat treatment. FIG. 8 shows the results of its X-ray diffraction.
第２表
第２表は、得られた有色酸化チタンの色調をＪＩＳＺ８
７２９により測定した結果をＬ“ａ０ｂ１表示系で示し
ている。比較のため、一般に使用されているカーボンブ
ランク、墨色酸化鉄、及び従来のチタンブラック（Ｔｉ
Ｏ）を同様に測定し、色調を示した。この実施例では反
応温度が高くなるに従って色彩は灰緑色から黒色に変化
しており、反応温度１２００ ’Ｃで得られた有色酸化
チタンは、明度がカーボンブラックと同等か、それ以下
の黒さであることがわかる。Table 2 Table 2 shows the color tone of the obtained colored titanium oxide according to JISZ8
729 is shown in the L"a0b1 display system. For comparison, commonly used carbon blanks, black iron oxide, and conventional titanium black (Ti
O) was measured in the same manner and the color tone was shown. In this example, the color changes from gray-green to black as the reaction temperature increases, and the colored titanium oxide obtained at the reaction temperature of 1200'C has a brightness equal to or lower than that of carbon black. I understand that there is something.
第９図は、反応温度１２００°Ｃで得られた有色酸化チ
タン粒子の電子顕微鏡によるＴＥＭを示すこの電子顕微
鏡による観察の結果から、平均粒子径が０．０５〜０．
２μ■と極めて小さい、超微粒子状のものであることが
わかる。FIG. 9 shows a TEM image taken using an electron microscope of colored titanium oxide particles obtained at a reaction temperature of 1200°C. From the results of observation using this electron microscope, it was found that the average particle diameter was 0.05-0.
It can be seen that the particles are extremely small, 2μ■, and are in the form of ultrafine particles.
第１０図は、反応温度１２００°Ｃで得られた有色酸化
チタン粒子の加熱による熱的挙動、重量変化量を確認す
るために行った熱分析の結果を示している。有色酸化チ
タンは４１３°Ｃと４５３°Ｃに発熱ピークを示し、高
温まで熱的に安定であり、４００″Ｃ付近から重量が増
加することが認められていた。これはＴｉＯが酸化され
てＴｉＯ□に戻るものと考えられる。FIG. 10 shows the results of thermal analysis conducted to confirm the thermal behavior and weight change due to heating of colored titanium oxide particles obtained at a reaction temperature of 1200°C. Colored titanium oxide shows exothermic peaks at 413°C and 453°C, is thermally stable up to high temperatures, and has been observed to increase in weight from around 400"C. This is because TiO is oxidized and TiO It is thought that it will return to □.
第１１図は反応温度１２００°Ｃで得られた有色酸化チ
タン粒子の赤外吸収スペクトルを示す。この結果から炭
化水素は生成していないものと考えられる。FIG. 11 shows an infrared absorption spectrum of colored titanium oxide particles obtained at a reaction temperature of 1200°C. From this result, it is considered that no hydrocarbons were produced.
（実施例３）
原料のチタンアルコキシドとして、チタンテトラエトキ
シド（以下ＴＴＥという）をエタノールで２倍に希釈し
、これをＴＴＥ換算で２５８／ｈ微細噴霧供給装置２へ
供給し、窒素ガス５セ／ｍｉｎをキャリアガスとして反
応管４内へ噴霧供給した。(Example 3) As a raw material titanium alkoxide, titanium tetraethoxide (hereinafter referred to as TTE) was diluted twice with ethanol, and this was supplied to the fine spray supply device 2 at a rate of 258/h in terms of TTE, and 5 cycles of nitrogen gas were added. /min was sprayed into the reaction tube 4 as a carrier gas.
反応管４内には、水素ガス７．５β／ｍｉｎを反応ガス
として供給し、反応温度１２００ ”Ｃで有色酸化チタ
ンを生成させた。Hydrogen gas was supplied into the reaction tube 4 at a rate of 7.5β/min as a reaction gas, and colored titanium oxide was produced at a reaction temperature of 1200''C.
第１２図に、得られた有色酸化チタンのＸ線回折の結果
を示している。この有色酸化チタンは、Ｔｉ、Ｏ９、Ｔ
ｉ、０．等の一最大Ｔｉ、０２□。FIG. 12 shows the results of X-ray diffraction of the obtained colored titanium oxide. This colored titanium oxide includes Ti, O9, T
i, 0. etc. One maximum Ti, 02□.
で表される低次酸化チタンである。この色調は第１表に
示したように青黒色である。粒子径、粒子形状は実施例
１の反応温度１２００″Ｃで得られたものとほぼ同様で
あった。It is a lower titanium oxide represented by This color tone is blue-black as shown in Table 1. The particle diameter and particle shape were almost the same as those obtained in Example 1 at a reaction temperature of 1200''C.
（実施例４）
実施例３と同様の原料を用い、キャリアガスを窒素ガス
５ｆ／ｍｉｎ、反応ガスをアンモニアガス２゜２Ｌ／ｗ
ｉｎとし、反応温度１２００’Ｃで実施した。(Example 4) Using the same raw materials as in Example 3, the carrier gas was nitrogen gas at 5f/min, and the reaction gas was ammonia gas at 2°2L/w.
The reaction temperature was 1200'C.
得られた有色酸化チタンのＸ線回折の結果は、第１３図
に示している。この有色酸化チタンはＴｉＯであり、色
調は第２表に示すように黒色である。粒子径、粒子形状
は実施例２の反応温度１２００°Ｃで得られたものとほ
ぼ同様であった。The results of X-ray diffraction of the obtained colored titanium oxide are shown in FIG. This colored titanium oxide is TiO, and the color tone is black as shown in Table 2. The particle diameter and particle shape were almost the same as those obtained in Example 2 at a reaction temperature of 1200°C.
前記実施例１〜実施例４の反応温度１２００°Ｃで得ら
れた有色酸化チタン及び市販のＴｉＯ□の各サンプル０
．２ｇにイオン交換水を加えてそれぞれ全重量をＬｏｇ
としたもの、及び流動パラフィンを加えてそれぞれ全重
量を１０ｇとしたもの、をよく撹拌し、沈降速度を比較
した。全液面の高さを１００とした場合の沈降面で比較
すると、市販のＴ ｉ ０２は、イオン交換水、流動パ
ラフィンの何れにおいても、１時間で約９５％沈降した
。Each sample of colored titanium oxide obtained at the reaction temperature of 1200°C in Examples 1 to 4 and commercially available TiO□
．． Add ion exchange water to 2g and log the total weight of each
The mixture was thoroughly stirred, and the total weight was 10 g by adding liquid paraffin, and the sedimentation speeds were compared. Comparing the sedimentation surface when the height of the total liquid level is 100, commercially available T i 02 sedimented approximately 95% in 1 hour in both ion exchange water and liquid paraffin.
実施例２、実施例４の有色酸化チタンは、イオン交換水
では１０日で約４％しか沈降せず、流動パラフィンでは
１２時間で約−４％、１０日で約５０％の沈降であった
。実施例１、実施例３の有色酸化チタンは、イオン交換
水では１時間で約５０％、１２時間で約６０％の沈降で
あり、流動パラフィンでは、１２時間で約４％、２日で
約６０％の沈降であった。The colored titanium oxides of Examples 2 and 4 only settled about 4% in 10 days in ion-exchanged water, and about -4% in 12 hours and about 50% in 10 days in liquid paraffin. . The colored titanium oxides of Examples 1 and 3 settled approximately 50% in 1 hour and 60% in 12 hours in ion-exchanged water, and settled approximately 4% in 12 hours and approximately 60% in 2 days in liquid paraffin. The sedimentation was 60%.
このように、市販の′Ｆ１０□と比較すると、この有色
酸化チタンは、塗料や化粧品に混合した場合すくれた分
散性を示すものと考えられる。Thus, compared to commercially available 'F10□, this colored titanium oxide is considered to exhibit poor dispersibility when mixed into paints and cosmetics.
（発明の効果）
上述の如く、この発明の有色酸化チタンの製造方法によ
れば、粒子径が極めて小さく、粉砕工程が不要な有色酸
化チタンを連続的に製造することができ、生産性が向上
する。また、この方法で得られた有色酸化チタンは、色
調、熱安定性、分散性等、種々の特性にす（れており、
カーボンブラック、黒色顔料としてはもとより、吸着材
、触媒、帯電防止材等種々の用途に利用できる。(Effects of the Invention) As described above, according to the method for producing colored titanium oxide of the present invention, colored titanium oxide having an extremely small particle size and no pulverization process can be produced continuously, improving productivity. do. In addition, the colored titanium oxide obtained by this method has various properties such as color tone, thermal stability, and dispersibility.
It can be used not only as carbon black and black pigment, but also for various purposes such as adsorbents, catalysts, and antistatic materials.
第１図は、この発明の実施例に用いた製造装置の構成図
、第２図、第６図、第７図、第８図、第１２図及び第１
３図はこの発明の実施例で得られた有色酸化チタンのＸ
線回折パターン、第３図、第９図は粒子構造を示すもの
でいずれも５万倍の電子顕微鏡写真、第４図、第１０図
、は熱分析結果のグラフ、第５図、第１１図は赤外吸収
スペクトルを示す図である。
ｌ・・・・・・微量定量ポンプ、２・・・・・・微細噴
霧装置、・・・・・・キャリアガス導入口、４・・・・
・・反応管、・・・・・・補集装置、６・・・・・・ガ
ス吸収トラップ、・・・・・・反応ガス導入口、８・・
・・・・電気炉、・・・・・・連続取出装置。FIG. 1 is a block diagram of a manufacturing apparatus used in an embodiment of the present invention, FIG. 2, FIG. 6, FIG. 7, FIG. 8, FIG.
Figure 3 shows X of colored titanium oxide obtained in an example of this invention.
Linear diffraction patterns, Figures 3 and 9 are electron micrographs showing the particle structure, all magnified by 50,000 times, Figures 4 and 10 are graphs of thermal analysis results, Figures 5 and 11. is a diagram showing an infrared absorption spectrum. 1... Trace amount metering pump, 2... Fine spray device,... Carrier gas inlet, 4...
...Reaction tube, ...Collection device, 6...Gas absorption trap, ...Reaction gas inlet, 8...
...Electric furnace, ...Continuous extraction device.
Claims (3)
給して、分解還元反応を行なうことにより有色酸化チタ
ンの微粒子を連続的に生成させることを特徴とする有色
酸化チタンの製造方法。(1) A method for producing colored titanium oxide, which comprises continuously producing colored titanium oxide fine particles by spraying titanium alkoxide into a reducing gas atmosphere and carrying out a decomposition-reduction reaction.
いて行なうことを特徴とする請求項（１）記載の有色酸
化チタンの製造方法。(2) The method for producing colored titanium oxide according to claim (1), wherein the titanium alkoxide is supplied using an ultrafine atomizer.
で行なうことを特徴とする請求項（１）または（２）記
載の有色酸化チタンの製造方法。(3) The method for producing colored titanium oxide according to claim (1) or (2), wherein the titanium alkoxide is decomposed at a temperature of 800° C. or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2152264A JPH0637298B2 (en) | 1990-06-11 | 1990-06-11 | Method for producing colored titanium oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2152264A JPH0637298B2 (en) | 1990-06-11 | 1990-06-11 | Method for producing colored titanium oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0446016A true JPH0446016A (en) | 1992-02-17 |
| JPH0637298B2 JPH0637298B2 (en) | 1994-05-18 |
Family
ID=15536692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2152264A Expired - Fee Related JPH0637298B2 (en) | 1990-06-11 | 1990-06-11 | Method for producing colored titanium oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0637298B2 (en) |
-
1990
- 1990-06-11 JP JP2152264A patent/JPH0637298B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0637298B2 (en) | 1994-05-18 |
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