JP2003327432A - Low halogen-low rutile type hyperfine-grained titanium oxide and production method thereof - Google Patents
Low halogen-low rutile type hyperfine-grained titanium oxide and production method thereofInfo
- Publication number
- JP2003327432A JP2003327432A JP2003060147A JP2003060147A JP2003327432A JP 2003327432 A JP2003327432 A JP 2003327432A JP 2003060147 A JP2003060147 A JP 2003060147A JP 2003060147 A JP2003060147 A JP 2003060147A JP 2003327432 A JP2003327432 A JP 2003327432A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- halogen
- titanium
- gas
- producing
- 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 titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 389
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 296
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 102
- 239000007789 gas Substances 0.000 claims abstract description 97
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 62
- 150000002367 halogens Chemical class 0.000 claims abstract description 62
- 238000010438 heat treatment Methods 0.000 claims abstract description 35
- 230000001590 oxidative effect Effects 0.000 claims abstract description 35
- -1 titanium halide Chemical class 0.000 claims abstract description 33
- 239000010936 titanium Substances 0.000 claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims description 116
- 239000000460 chlorine Substances 0.000 claims description 110
- 229910052801 chlorine Inorganic materials 0.000 claims description 110
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 108
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 39
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 38
- 238000009826 distribution Methods 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 18
- 230000001186 cumulative effect Effects 0.000 claims description 14
- 239000012071 phase Substances 0.000 claims description 14
- 239000011941 photocatalyst Substances 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 8
- 229910001882 dioxygen Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 229920002379 silicone rubber Polymers 0.000 claims description 5
- 239000004945 silicone rubber Substances 0.000 claims description 5
- 238000000108 ultra-filtration Methods 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000007900 aqueous suspension Substances 0.000 claims description 3
- 239000003989 dielectric material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001223 reverse osmosis Methods 0.000 claims description 3
- 239000012808 vapor phase Substances 0.000 abstract description 17
- 238000005695 dehalogenation reaction Methods 0.000 abstract description 6
- 239000011882 ultra-fine particle Substances 0.000 description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 238000006298 dechlorination reaction Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000000149 argon plasma sintering Methods 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000691 measurement method Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 235000010724 Wisteria floribunda Nutrition 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002595 Dielectric elastomer Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 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
- 239000000049 pigment Substances 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Landscapes
- Hybrid Cells (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光触媒や太陽電
池、シリコーンゴムへの添加剤、誘電体用途等に好適な
低ルチル型の低塩素超微粒子酸化チタン及びその製造方
法に関する。さらに詳しくは、ハロゲンチタンを含むガ
スを酸化性ガスで高温酸化することにより得られる気相
法酸化チタンにおいて、ハロゲン含有量が低く、残存し
たハロゲンの除去も容易で、かつ、分散性の良い低ルチ
ル型の低ハロゲン超微粒子酸化チタン及びその製造方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low rutile type low chlorine ultrafine particle titanium oxide suitable for photocatalysts, solar cells, additives to silicone rubber, dielectric applications and the like, and a method for producing the same. More specifically, in a vapor-phase method titanium oxide obtained by high-temperature oxidizing a gas containing titanium halide with an oxidizing gas, the halogen content is low, residual halogen can be easily removed, and the dispersibility is low. The present invention relates to a rutile type low halogen ultrafine particle titanium oxide and a method for producing the same.
【０００２】[0002]
【従来の技術】超微粒子酸化チタンは、紫外線遮蔽材や
シリコーンゴムヘの添加剤、誘電体原料、化粧料等、多
岐の用途に亘って使用されてきた（酸化チタンは日本工
業規格（ＪＩＳ）には二酸化チタンと記載されており、
一般名として酸化チタンが広く使用されているので本明
細書中では酸化チタンと略称する）。また、酸化チタン
は光触媒や、太陽電池等としても応用される。2. Description of the Related Art Ultrafine particle titanium oxide has been used for a wide variety of purposes such as ultraviolet shielding materials, additives to silicone rubber, dielectric materials, cosmetics, etc. (Titanium oxide is a Japanese Industrial Standard (JIS) Is described as titanium dioxide,
Since titanium oxide is widely used as a general name, it is abbreviated as titanium oxide in the present specification). Titanium oxide is also applied as a photocatalyst, a solar cell, and the like.
【０００３】酸化チタンの結晶型にはルチル型、アナタ
ーゼ型、ブルッカイト型の３種類が存在するが、このう
ち、前述の光触媒、太陽電池用途の分野ではルチル型よ
りも光電気化学活性に優れるアナターゼ型やブルッカイ
ト型が用いられる。There are three types of titanium oxide, namely, rutile type, anatase type, and brookite type. Of these, anatase, which is superior in photoelectrochemical activity to rutile type, is used in the fields of photocatalyst and solar cell applications. Type and brookite type are used.
【０００４】酸化チタンの光触媒作用は抗菌タイル、セ
ルフ・クリーニング建材、消臭繊維など、有機物の分解
に利用されており、その機構は次のように説明されてい
る。酸化チタンは紫外線を吸収し、その内部に電子と正
孔を発生させる。正孔は酸化チタンの吸着水と反応して
ヒドロキシラジカルを生成させ、酸化チタン粒子表面に
吸着した有機物を炭酸ガスや水に分解する（「光クリー
ン革命」藤嶋昭、橋本和仁、渡部俊也共著，（株）シー
エムシー，143−145頁（１９９７））。すなわち、光触
媒作用の強い酸化チタンの条件として、正孔を発生させ
やすいこと、酸化チタン表面に正孔が到達しやすいこ
と、が挙げられる。「酸化チタン光触媒のすべて」（橋
本和仁、藤嶋昭 編集，（株）シーエムシー，29−30頁
（１９９８））には、光触媒作用が高い酸化チタンとし
て、アナターゼ型酸化チタン、格子欠陥の少ない酸化チ
タン、粒子が小さく比表面積の大きい酸化チタンが挙げ
られている。The photocatalytic action of titanium oxide is utilized for the decomposition of organic substances such as antibacterial tiles, self-cleaning building materials, and deodorant fibers, and the mechanism thereof is explained as follows. Titanium oxide absorbs ultraviolet rays and generates electrons and holes therein. The holes react with the adsorbed water of titanium oxide to generate hydroxy radicals, and decompose the organic substances adsorbed on the surface of the titanium oxide particles into carbon dioxide gas and water (“Light Clean Revolution” Akira Fujishima, Kazuhito Hashimoto, Toshiya Watanabe, CMC, pages 143-145 (1997)). That is, the conditions for titanium oxide having a strong photocatalytic action are that holes are easily generated and holes easily reach the surface of titanium oxide. "All about titanium oxide photocatalyst" (Kazuhito Hashimoto, Akira Fujishima, edited, CMC Co., Ltd., pp. 29-30 (1998)) describes titanium oxide with high photocatalytic activity, anatase-type titanium oxide, and oxidation with few lattice defects. Titanium and titanium oxide with small particles and large specific surface area are mentioned.
【０００５】太陽電池としての応用は、１９９１年にロ
ーザンヌ工科大学のグレッツエルらが酸化チタンとルテ
ニウム系色素を組み合わせた色素増感型太陽電池を報告
して以来、研究が進められている（Ｍ．Ｇｒａｅｚｅ
ｌ，Ｎａｔｕｒｅ，３５３，７３７，（１９９１））。
前記色素増感型太陽電池において、酸化チタンは色素の
担持体及びｎ型半導体としての役割を有し、導電性ガラ
ス電極に結着された色素電極として用いられる。色素増
感型太陽電池は電解層を色素電極と対極で挟み込んだ構
造であり、色素は光を吸収することで電子と正孔を発生
する。発生した電子は酸化チタン層を通じて導電性ガラ
ス電極に到達し、外部へと取り出される。一方、発生し
た正孔は、電解層を通じて対極へと運ばれ、導電性ガラ
ス電極を通じて供給された電子と結合する。色素増感型
太陽電池の特性を高める一因として、酸化チタンと色素
の結合が容易であることが挙げられる。色素との結合が
容易な酸化チタンの結晶型としては、例えば、特開平１
０−２５５８６３号公報にはアナターゼが使用されてお
り、また、特開２０００−３４０２６９号公報にはブル
ッカイトが色素増感型太陽電池に好適であることが記載
されている。The application as a solar cell has been studied since 1991 when Gretzel et al. Of Lausanne Institute of Technology reported a dye-sensitized solar cell in which titanium oxide and a ruthenium dye were combined (M. Graeze
1, Nature, 353, 737, (1991)).
In the dye-sensitized solar cell, titanium oxide serves as a dye carrier and an n-type semiconductor, and is used as a dye electrode bound to a conductive glass electrode. A dye-sensitized solar cell has a structure in which an electrolytic layer is sandwiched between a dye electrode and a counter electrode, and the dye absorbs light to generate electrons and holes. The generated electrons reach the conductive glass electrode through the titanium oxide layer and are taken out to the outside. On the other hand, the generated holes are carried to the counter electrode through the electrolytic layer and combine with the electrons supplied through the conductive glass electrode. One of the factors that enhance the characteristics of the dye-sensitized solar cell is that titanium oxide and the dye can be easily bonded. As a crystal form of titanium oxide which can be easily bonded to a dye, for example, JP-A-1
Anatase is used in JP-A No. 0-255863 and JP-A No. 2000-340269 describes that brookite is suitable for a dye-sensitized solar cell.
【０００６】酸化チタンは分散性の良いものがその機能
を引き出す上で重要である。例えば酸化チタンを光触媒
として使用する際、分散性が悪いと隠蔽力が強くなるた
め、使用できる用途が限定されてしまう。太陽電池の分
野においても分散性の悪い酸化チタンは光を透過しにく
いため、光吸収に寄与できる酸化チタンが限られ、光電
変換効率を悪化させる。一般に、光散乱（隠蔽力）は粒
径が可視光波長の１／２程度であるとき最大になり、粒
径が小さくなると光散乱も弱まるといわれている（「酸
化チタン」清野学著，技報堂（株），ｐ．１２９，（１
９９１））。前述の分野で利用される酸化チタンの一次
粒子径は数〜数十ｎｍであることが多いため分散性が良
好であれば光散乱への影響は小さい。しかし、分散が悪
く凝集粒径の大きい酸化チタンは光散乱が強まることに
なる。Titanium oxide having a good dispersibility is important for bringing out its function. For example, when titanium oxide is used as a photocatalyst, if the dispersibility is poor, the hiding power becomes strong, so that the usable applications are limited. Even in the field of solar cells, titanium oxide, which has poor dispersibility, does not easily transmit light, so that the titanium oxide that can contribute to light absorption is limited and the photoelectric conversion efficiency is deteriorated. Generally, it is said that the light scattering (hiding power) is maximized when the particle size is about 1/2 of the visible light wavelength, and the light scattering is weakened when the particle size is reduced ("Titanium oxide", written by Manabu Seino, Gihodo). Ltd., p.129, (1
991)). Since the primary particle diameter of titanium oxide used in the aforementioned fields is often several to several tens of nm, if the dispersibility is good, the influence on light scattering is small. However, titanium oxide, which is poorly dispersed and has a large agglomerated particle size, has an increased light scattering.
【０００７】以上の理由から上記分野では、酸化チタン
には高分散性が要求され、分散性の良いアナターゼ型あ
るいはブルッカイト型の超微粒子酸化チタンが使用され
る。一般に、超微粒子の１次粒子径は、明確にされてい
ないが、通常約０．１μｍ以下の微粒子に対して呼称さ
れる。For the above reasons, in the above field, titanium oxide is required to have high dispersibility, and anatase type or brookite type ultrafine particle titanium oxide having good dispersibility is used. Generally, the primary particle size of ultrafine particles is not clarified, but is usually referred to as fine particles of about 0.1 μm or less.
【０００８】酸化チタンを光触媒、太陽電池で使用する
場合、塩素のように腐食性を有する成分が存在すると基
材を腐食させたり、変質させたりするため、酸化チタン
の塩素含有量は低く抑える必要がある。また、Ｆｅ、Ａ
ｌ、Ｓｉ、Ｓ等も低く抑えた方が良い。例えば、酸化チ
タン中のＦｅが多すぎると着色の原因になり、透明性を
要求される用途での使用に適さない。酸化チタン粒子内
部のＡｌ、Ｓ等の成分が多すぎると格子欠陥を生じてし
まい、光触媒、太陽電池としての機能を低下させること
も考えられる。When titanium oxide is used in a photocatalyst or a solar cell, the presence of a corrosive component such as chlorine causes the base material to be corroded or deteriorated. Therefore, it is necessary to keep the chlorine content of titanium oxide low. There is. In addition, Fe, A
It is better to keep l, Si, S, etc. low. For example, if too much Fe in titanium oxide causes coloring, it is not suitable for use in applications where transparency is required. If the amount of Al, S, etc. in the titanium oxide particles is too large, lattice defects may occur and the functions of the photocatalyst and the solar cell may be deteriorated.
【０００９】酸化チタンの製造方法は、大別して四塩化
チタンや硫酸チタニルを加水分解する液相法と、ハロゲ
ン化チタンを酸素あるいは水蒸気等の酸化性ガスと反応
させる気相法とがある。液相法による酸化チタンはアナ
ターゼを主相として得ることはできるが、ゾルあるいは
スラリー状態にならざるを得ない。この状態で使用する
場合、用途は限定される。粉末として使用するためには
乾燥させる必要があり、溶媒に濡れた超微粒子は乾燥が
進むに連れて凝集が激しくなる（「超微粒子ハンドブッ
ク」斎藤進六監修、フジ・テクノシステム、388頁、
（１９９０）。この酸化チタンを光触媒等に供する場合
には分散性を高めるため酸化チタンを強く解砕したり粉
砕する必要があり、粉砕等の処理に由来する摩耗物の混
入や粒度分布の不均一さ等の問題を引き起こすことがあ
る。The method for producing titanium oxide is roughly classified into a liquid phase method in which titanium tetrachloride or titanyl sulfate is hydrolyzed and a gas phase method in which titanium halide is reacted with an oxidizing gas such as oxygen or water vapor. Titanium oxide obtained by the liquid phase method can obtain anatase as a main phase, but it is inevitably in a sol or slurry state. When used in this state, the use is limited. In order to use it as a powder, it needs to be dried, and the ultrafine particles wet with the solvent become more agglomerated as the drying progresses ("Ultrafine particle handbook" supervised by Shinroku Saito, Fuji Techno System, p. 388,
(1990). When this titanium oxide is used as a photocatalyst, etc., it is necessary to strongly disintegrate or pulverize the titanium oxide in order to enhance dispersibility, and it is necessary to disperse wear particles derived from the treatment such as pulverization and nonuniform particle size distribution. May cause problems.
【００１０】一般的に、気相法による酸化チタンは、溶
媒を使用しないため液相法に比べて分散性に優れてい
る。Generally, titanium oxide prepared by the vapor phase method is superior in dispersibility to the liquid phase method because it does not use a solvent.
【００１１】気相法で酸化チタンの超微粒子を得る例は
数多くあり、例えば、特開平６−３４０４２３号公報で
は、四塩化チタンを火炎中にて加水分解し酸化チタンを
製造する方法において、酸素、四塩化チタン、水素のモ
ル比を調整して反応させ、ルチル含有率の高い酸化チタ
ンを得る方法が開示されている。特開平７−３１６５３
６号公報には四塩化チタンを高温気相中で加水分解さ
せ、反応生成物を急速に冷却することにより、結晶質酸
化チタン粉末を製造する方法において、炎温度と原料ガ
ス中のチタン濃度を特定することにより平均一次粒子径
が４０ｎｍ以上、１５０ｎｍ以下の結晶質透明酸化チタ
ンを得る方法が開示されている。しかし、何れの場合も
微粒子ではあるがルチル含有率の高い酸化チタンしか得
られていなく、光触媒用途、太陽電池用途として使用す
るには適さない。There are many examples of obtaining ultrafine particles of titanium oxide by a vapor phase method. For example, in JP-A-6-340423, in a method for producing titanium oxide by hydrolyzing titanium tetrachloride in a flame, oxygen is used. , Titanium tetrachloride and hydrogen are adjusted and reacted to obtain titanium oxide having a high rutile content. Japanese Patent Laid-Open No. 7-31653
No. 6 discloses a method for producing crystalline titanium oxide powder by hydrolyzing titanium tetrachloride in a high-temperature gas phase and rapidly cooling the reaction product, the flame temperature and the titanium concentration in the raw material gas. A method for obtaining crystalline transparent titanium oxide having an average primary particle diameter of 40 nm or more and 150 nm or less by specifying is disclosed. However, in all cases, only fine particles of titanium oxide having a high rutile content are obtained, which is not suitable for use as a photocatalyst or a solar cell.
【００１２】気相法でアナターゼが主相の酸化チタンを
製造する方法は、例えば、特開平３−２５２３１５号公
報には気相反応において酸素と水素の混合気体中の水素
の比率を変えることでルチルの含有比率を調整する製造
方法が開示されており、ルチル含有率が９％の酸化チタ
ンが記載されている。しかし、例示された酸化チタンの
粒径は０．５〜０．６μｍであり、一般的に超微粒子と
いわれる粒径の範囲よりも粗い。A method for producing titanium oxide having anatase as a main phase by a vapor phase method is disclosed in, for example, JP-A-3-252315, by changing the ratio of hydrogen in a mixed gas of oxygen and hydrogen in a gas phase reaction. A production method for adjusting the content ratio of rutile is disclosed, and titanium oxide having a rutile content of 9% is described. However, the particle size of the exemplified titanium oxide is 0.5 to 0.6 μm, which is coarser than the range of particle size generally called ultrafine particles.
【００１３】ハロゲン化チタンを原料とする気相法で酸
化チタンを製造すると超微粒子は得やすいが、原料由来
のハロゲンが酸化チタンに残存するため、加熱あるいは
水洗等による脱ハロゲンが必要となることが多い。しか
し、超微粒子酸化チタンは低ハロゲン化のための加熱に
よって粒子同士の焼結が進行し比表面積が低下しやすく
なる上、アナターゼ型からルチル型への結晶型の転移が
生じてしまうことがある。比表面積の低下、結晶転移を
抑制するためには低温あるいは短時間の加熱を行わざる
を得ないが、充分に脱ハロゲンできなくなる。超微粒子
酸化チタンの低塩素化法は、例えば、特開平１０−２５
１０２１号公報に開示されている。この方法は、酸化チ
タンを円筒形回転式加熱炉中で転動させながら水蒸気と
接触させ、塩素含有量を低くする方法である。また、こ
れに記載されている酸化チタンのルチル含有率は１５％
と高いものであった。When titanium oxide is produced by a vapor phase method using titanium halide as a raw material, ultrafine particles are easily obtained, but since halogen derived from the raw material remains in titanium oxide, dehalogenation by heating or washing with water is required. There are many. However, in the case of ultrafine titanium oxide, the heating for reducing the halogen causes the particles to sinter with each other and the specific surface area tends to decrease, and the anatase-type to rutile-type transition may occur. . In order to suppress the decrease of the specific surface area and the crystal transition, heating at low temperature or for a short time is unavoidable, but sufficient dehalogenation cannot be achieved. A method of reducing the chlorine content of ultrafine titanium oxide is disclosed in, for example, JP-A-10-25
It is disclosed in Japanese Patent No. 1021. This method is a method in which titanium oxide is brought into contact with water vapor while rolling in a cylindrical rotary heating furnace to reduce the chlorine content. Further, the rutile content of titanium oxide described therein is 15%.
It was expensive.
【００１４】一方、水洗等による脱ハロゲンでは酸化チ
タン粒子表面に残存したハロゲンを除去することはでき
るが、粒子内部のハロゲンは水と接触しにくいため、内
部ハロゲンが残存しやすいという問題があった。On the other hand, although halogen remaining on the surface of titanium oxide particles can be removed by dehalogenation by washing with water or the like, there is a problem that the internal halogen is likely to remain because the halogen inside the particle is difficult to contact with water. .
【００１５】これらのように従来の気相法において、ハ
ロゲン含有量の低い低ルチル型の超微粒子酸化チタンは
得られていなかった。As described above, low rutile type ultrafine titanium oxide particles having a low halogen content have not been obtained by the conventional vapor phase method.
【特許文献１】特開平１０−２５５８６３号公報[Patent Document 1] Japanese Patent Laid-Open No. 10-255863
【特許文献２】特開２０００−３４０２６９号公報[Patent Document 2] Japanese Patent Laid-Open No. 2000-340269
【特許文献３】特開平６−３４０４２３号公報[Patent Document 3] JP-A-6-340423
【特許文献４】特開平７−３１６５３６号公報[Patent Document 4] Japanese Unexamined Patent Publication No. 7-316536
【特許文献５】特開平１０−２５１０２１号公報[Patent Document 5] Japanese Patent Laid-Open No. 10-251021
【非特許文献１】「光クリーン革命」藤嶋昭、橋本和
仁、渡部俊也共著，（株）シーエムシー，143−145頁
（１９９７）[Non-Patent Document 1] "Light Clean Revolution" Akira Fujishima, Kazuhito Hashimoto, Toshiya Watanabe, CMC, pp.143-145 (1997)
【非特許文献２】「酸化チタン光触媒のすべて」（橋本
和仁、藤嶋昭 編集，（株）シーエムシー，29−30頁
（１９９８））[Non-patent document 2] "All about titanium oxide photocatalyst" (Kazuhito Hashimoto, Akira Fujishima, CMC, pp. 29-30 (1998))
【非特許文献３】Ｍ．Ｇｒａｅｚｅｌ，Ｎａｔｕｒｅ，
３５３，７３７，（１９９１）[Non-Patent Document 3] Graezel, Nature,
353, 737, (1991)
【非特許文献４】「酸化チタン」清野学著，技報堂
（株），ｐ．１２９，（１９９１）[Non-patent document 4] "Titanium oxide" by Manabu Seino, Gihodo Co., Ltd., p. 129, (1991)
【非特許文献５】（「超微粒子ハンドブック」斎藤進六
監修、フジ・テクノシステム、388頁、（１９９０）[Non-patent document 5] ("Ultra-fine particle handbook", supervised by Shinroku Saito, Fuji Techno System, page 388, (1990)
【００１６】[0016]
【発明が解決しようとする課題】本発明は上記問題点を
解決すべくなされたものであり、本発明の課題は、気相
法において、分散性に優れ、かつハロゲン含有量の低い
低ルチル型の超微粒子酸化チタン及びその製造方法を提
供することにある。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a low rutile type which is excellent in dispersibility and has a low halogen content in a vapor phase method. Another object of the present invention is to provide an ultrafine particle titanium oxide and a method for producing the same.
【００１７】[0017]
【課題を解決するための手段】本発明者らは、上記課題
に鑑み鋭意研究した結果、気相法において分散性に優
れ、かつ、ハロゲン含有量の低い低ルチル型の超微粒子
酸化チタンを製造し得ることを見出し、上記課題を解決
するに至った。DISCLOSURE OF THE INVENTION As a result of intensive studies in view of the above-mentioned problems, the present inventors produced low rutile type ultrafine particle titanium oxide having excellent dispersibility in a gas phase method and having a low halogen content. They have found that they can do so and have solved the above problems.
【００１８】本発明は、ハロゲン化チタンを含有するガ
ス及び酸化性ガス（酸素または水蒸気もしくはこれらを
含有する混合ガス）を反応させる気相法において、該原
料ガスを加熱温度、加熱時間を制御しながら反応させた
後、脱ハロゲンすることにより得られる、ルチル含有率
が５％以下の酸化チタンであって、かつ、高いＢＥＴ比
表面積及び特定の特性を有する低ルチル型の超微粒子酸
化チタン及びその製造方法を提供するものである。The present invention is a gas phase method in which a gas containing titanium halide and an oxidizing gas (oxygen or water vapor or a mixed gas containing these) are reacted to control the heating temperature and heating time of the source gas. And a low rutile-type ultrafine particle titanium oxide having a rutile content of 5% or less and having a high BET specific surface area and specific characteristics, which is obtained by dehalogenation after the reaction. A manufacturing method is provided.
【００１９】すなわち本発明は、以下の発明を含む。
（１）ハロゲン化チタンを含むガスと酸化性ガスとを反
応させることにより得られる酸化チタンであって、ルチ
ル含有率が５％以下で、かつ、ＢＥＴ一点法で測定した
酸化チタンの比表面積をＢ（ｍ2／ｇ）、酸化チタンの
全ハロゲン含有量をＣ（質量ｐｐｍ）としたとき、
Ｃ≦６５０ｅ0.02B
で示され、且つ、１質量％の水懸濁液とした時に、その
水懸濁液を２０℃で３０分間放置後、酸化チタンに含ま
れていたハロゲン量の８０質量％以上のハロゲンが液相
に移行することを特徴とする酸化チタン。
（２）酸化チタンに含まれていたハロゲン量の９０質量
％以上のハロゲンが液相に移行する上記（１）に記載の
酸化チタン。
（３）酸化チタンが、Ｆｅ、Ａｌ、Ｓｉ及びＳの各元素
をそれぞれ１００質量ｐｐｍ以下含む上記（１）または
（２）に記載の酸化チタン。
（４）酸化チタンが、１０〜２００ｍ2／ｇの比表面積
を持つ上記（１）〜（３）に記載の酸化チタン。
（５）酸化チタンの主相が、アナターゼである上記
（１）〜（４）のいずれか１項に記載の酸化チタン。
（６）酸化チタンのアナターゼ含有率が、９０％以上で
ある上記（５）に記載の酸化チタン。
（７）酸化チタンの主相が、ブルッカイトである上記
（１）〜（４）のいずれか１項に記載の酸化チタン。
（８）酸化チタンのブルッカイト含有率が９０％以上で
ある上記（７）の酸化チタン。
（９）酸化チタンが、レーザー回折式粒度分析計によっ
て測定される２．５μｍ以下の９０％累積質量粒度分布
径を持つ、上記（１）〜（８）のいずれか１項に記載の
酸化チタン。
（１０）前記ハロゲン化チタンが四塩化チタンであり、
前記ハロゲンが塩素である上記（１）〜（９）のいずれ
か１項に記載の酸化チタン。
（１１）ハロゲン化チタンを含むガスと酸化性ガスとを
反応させることにより酸化チタンを製造する気相法にお
いて、ハロゲン化チタンを含むガス及び酸化性ガスをそ
れぞれ反応器に導入し反応させたとき、該反応器内の温
度が８００℃以上１，１００℃未満であることを特徴と
する酸化チタンの製造方法。
（１２）ハロゲン化チタンを含むガス及び酸化性ガス
が、反応器内で８００℃以上１，１００℃未満の温度の
滞留時間が０．１秒以下である上記（１１）に記載の酸
化チタンの製造方法。
（１３）ハロゲン化チタンを含むガス及び酸化性ガス
が、それぞれ、６００℃以上、１，１００℃未満に予熱
されて反応器に導入される上記（１１）または（１２）
に記載の酸化チタンの製造方法。
（１４）反応が、ハロゲン化チタン１モルに対し不活性
ガス０．１〜２０モルの割合で混合した原料ガスと、ハ
ロゲン化チタン１モルに対し１〜３０モルの酸化性ガス
とで行われる上記（１１）〜（１３）のいずれか１項に
記載の酸化チタンの製造方法。
（１５）酸化性ガスが、水蒸気を含む酸素ガスであるこ
とを特徴とする上記（１１）〜（１４）のいずれか１項
に記載の酸化チタンの製造方法。
（１６）酸化性ガスが、酸素ガス１モルに対し、水蒸気
０．１モル以上を含む上記（１５）に記載の酸化チタン
の製造方法。
（１７）前記ハロゲン化チタンが四塩化チタンである上
記（１１）〜（１６）のいずれか１項に記載の酸化チタ
ンの製造方法。
（１８）上記（１１）〜（１７）のいずれか１項に記載
の製造方法で製造された酸化チタンを乾式でハロゲンを
除去することを特徴とする酸化チタンの製造方法。
（１９）乾式でハロゲンを除去する方法が、酸化チタン
を２００〜５００℃に加熱することにより行う方法であ
る上記（１８）に記載の酸化チタンの製造方法。
（２０）乾式でハロゲンを除去する方法が、水蒸気を含
有するガスを２００〜１０００℃に加熱し、酸化チタン
と接触させながら行なう方法である上記（１８）に記載
の酸化チタンの製造方法。
（２１）水蒸気を含有するガスが、水蒸気を０．１容量
％以上含む空気である上記（２０）に記載の酸化チタン
の製造方法。
（２２）水蒸気が、酸化チタンに対し質量比で０．０１
以上である上記（２０）に記載の酸化チタンの製造方
法。
（２３）上記（１１）〜（１７）のいずれか１項に記載
の製造方法で製造された酸化チタンを湿式でハロゲンを
除去し、酸化チタンを含むスラリーを得ることを特徴と
する酸化チタンの製造方法。
（２４）湿式でハロゲンを除去する方法が、酸化チタン
を水に懸濁させ、液相に移行したハロゲンを系外に分離
する方法である上記（２３）に記載の酸化チタンの製造
方法。
（２５）湿式でハロゲンを除去する方法が、ハロゲンの
分離を限外ろ過膜で行う方法である上記（２３）または
（２４）に記載の酸化チタンの製造方法。
（２６）湿式でハロゲンを除去する方法が、ハロゲンの
分離を逆浸透膜で行う方法である上記（２３）または
（２４）に記載の酸化チタンの製造方法。
（２７）湿式でハロゲンを除去する方法が、ハロゲンの
分離をフィルタープレスで行う方法である上記（２３）
または（２４）に記載の酸化チタンの製造方法。
（２８）上記（１１）〜（２７）のいずれか１項に記載
の製造方法で製造された酸化チタンを含むことを特徴と
する粉体。
（２９）上記（１１）〜（２７）のいずれか１項に記載
の製造方法で製造された酸化チタンを含むことを特徴と
するスラリー。
（３０）上記（１１）〜（２７）のいずれか１項に記載
の製造方法で製造された酸化チタンを含むことを特徴と
する組成物。
（３１）上記（１１）〜（２７）のいずれか１項に記載
の製造方法で製造された酸化チタンを含むことを特徴と
する光触媒材料。
（３２）上記（１１）〜（２７）のいずれか１項に記載
の製造方法で製造された酸化チタンを含むことを特徴と
する湿式太陽電池用材料。
（３３）上記（１１）〜（２７）のいずれか１項に記載
の製造方法で製造された酸化チタンを含むことを特徴と
する誘電体原料。
（３４）上記（１１）〜（２７）のいずれか１項に記載
の製造方法で製造された酸化チタンを含むことを特徴と
するシリコーンゴム添加剤。
（３５）ルチル含有率が５％以下、ＢＥＴ一点法で測定
した比表面積が１０〜２００ｍ2／ｇ、レーザー回折式
粒度分析計によって測定される９０％累積質量粒度分布
径が２．５μｍ以下の酸化チタン粒子であり、かつ、Ｂ
ＥＴ一点法で測定した酸化チタンの比表面積をＢ（ｍ2
／ｇ）、酸化チタン粒子内部のハロゲン含有量をＣ
i（質量ｐｐｍ）としたとき、粒子内部に含まれるハロ
ゲン量が０≦Ｃi≦６５０ｋｅ0.02B（ｋは０．２０）で
示されることを特徴とする酸化チタン粒子。
（３６）１０＜Ｃi≦６５０ｋｅ0.02B（ｋは０．１５）
で示される量のハロゲンを粒子内部に含む上記（３５）
に記載の酸化チタン粒子。That is, the present invention includes the following inventions. (1) A titanium oxide obtained by reacting a gas containing titanium halide with an oxidizing gas, wherein the rutile content is 5% or less and the specific surface area of titanium oxide measured by the BET single point method is When B (m 2 / g) and the total halogen content of titanium oxide are C (mass ppm), C ≦ 650e 0.02 B , and when 1% by mass of water suspension is used, Titanium oxide characterized in that after the suspension is left at 20 ° C. for 30 minutes, 80% by mass or more of the halogen contained in titanium oxide moves to the liquid phase. (2) The titanium oxide as described in (1) above, wherein 90% by mass or more of the halogen amount contained in the titanium oxide is transferred to the liquid phase. (3) The titanium oxide as described in (1) or (2) above, wherein the titanium oxide contains 100 mass ppm or less of each element of Fe, Al, Si and S. (4) The titanium oxide as described in (1) to (3) above, which has a specific surface area of 10 to 200 m 2 / g. (5) The titanium oxide according to any one of (1) to (4) above, wherein the main phase of titanium oxide is anatase. (6) The titanium oxide according to (5) above, wherein the titanium oxide has an anatase content of 90% or more. (7) The titanium oxide as described in any one of (1) to (4) above, wherein the main phase of titanium oxide is brookite. (8) The titanium oxide according to (7) above, wherein the brookite content of titanium oxide is 90% or more. (9) Titanium oxide according to any one of (1) to (8), wherein the titanium oxide has a 90% cumulative mass particle size distribution diameter of 2.5 μm or less measured by a laser diffraction particle size analyzer. . (10) The titanium halide is titanium tetrachloride,
The titanium oxide according to any one of (1) to (9) above, wherein the halogen is chlorine. (11) In a gas phase method for producing titanium oxide by reacting a gas containing titanium halide with an oxidizing gas, when a gas containing titanium halide and an oxidizing gas are introduced into a reactor and reacted. A method for producing titanium oxide, wherein the temperature in the reactor is 800 ° C. or higher and lower than 1,100 ° C. (12) The titanium oxide according to (11) above, wherein the gas containing titanium halide and the oxidizing gas have a residence time of 0.1 second or less at a temperature of 800 ° C. or higher and lower than 1,100 ° C. in the reactor. Production method. (13) The above-mentioned (11) or (12), in which the gas containing titanium halide and the oxidizing gas are respectively preheated to 600 ° C. or higher and lower than 1,100 ° C. and introduced into the reactor.
The method for producing titanium oxide according to. (14) The reaction is carried out with a raw material gas mixed with 0.1 mol of an inert gas in an amount of 0.1 to 20 mol with respect to 1 mol of a titanium halide and with an oxidizing gas in an amount of 1 to 30 mol with respect to 1 mol of a titanium halide. The method for producing titanium oxide according to any one of (11) to (13) above. (15) The method for producing titanium oxide as described in any one of (11) to (14) above, wherein the oxidizing gas is oxygen gas containing water vapor. (16) The method for producing titanium oxide according to (15) above, wherein the oxidizing gas contains 0.1 mol or more of water vapor with respect to 1 mol of oxygen gas. (17) The method for producing titanium oxide according to any one of (11) to (16) above, wherein the titanium halide is titanium tetrachloride. (18) A method for producing titanium oxide, characterized in that the titanium oxide produced by the method according to any one of (11) to (17) above is dried to remove halogen. (19) The method for producing titanium oxide according to the above (18), wherein the method of removing halogen by dry method is a method of heating titanium oxide to 200 to 500 ° C. (20) The method for producing titanium oxide according to the above (18), wherein the method for removing halogen by a dry method is a method in which a gas containing water vapor is heated to 200 to 1000 ° C. and brought into contact with titanium oxide. (21) The method for producing titanium oxide according to the above (20), wherein the gas containing water vapor is air containing 0.1% by volume or more of water vapor. (22) Water vapor is 0.01 in mass ratio to titanium oxide.
The above is the method for producing titanium oxide according to the above (20). (23) A titanium oxide produced by the production method according to any one of (11) to (17) above, wherein halogen is removed by a wet method to obtain a slurry containing titanium oxide. Production method. (24) The method for producing titanium oxide according to the above (23), wherein the method of removing halogen by a wet method is a method of suspending titanium oxide in water and separating the halogen transferred to the liquid phase out of the system. (25) The method for producing titanium oxide according to the above (23) or (24), wherein the method of removing halogen by a wet method is a method of separating halogen by an ultrafiltration membrane. (26) The method for producing titanium oxide according to the above (23) or (24), wherein the wet method for removing halogen is a method for separating halogen by a reverse osmosis membrane. (27) The method of removing halogen by a wet method is a method of separating halogen with a filter press. (23)
Alternatively, the method for producing titanium oxide according to (24). (28) A powder comprising the titanium oxide produced by the production method according to any one of (11) to (27). (29) A slurry comprising the titanium oxide manufactured by the manufacturing method according to any one of (11) to (27). (30) A composition comprising the titanium oxide produced by the production method according to any one of (11) to (27). (31) A photocatalyst material containing titanium oxide produced by the production method according to any one of (11) to (27). (32) A wet-type solar cell material containing titanium oxide produced by the production method according to any one of (11) to (27). (33) A dielectric material containing titanium oxide manufactured by the manufacturing method according to any one of (11) to (27). (34) A silicone rubber additive containing titanium oxide produced by the production method according to any one of (11) to (27). (35) The rutile content is 5% or less, the specific surface area measured by the BET single point method is 10 to 200 m 2 / g, and the 90% cumulative mass particle size distribution diameter measured by a laser diffraction type particle size analyzer is 2.5 μm or less. Titanium oxide particles and B
The specific surface area of titanium oxide measured by the ET one-point method is B (m 2
/ G) and the halogen content inside the titanium oxide particles is C
The titanium oxide particles are characterized in that the amount of halogen contained in the particles is 0 ≦ C i ≦ 650 ke 0.02 B (k is 0.20), where i (mass ppm). (36) 10 <C i ≦ 650 ke 0.02B (k is 0.15)
(35) containing halogen in an amount shown by
Titanium oxide particles according to.
【００２０】[0020]
【発明の実施の形態】本発明の酸化チタンの原料である
ハロゲン化チタンとしては、工業的に入手し易い塩化チ
タン、特に四塩化チタンが好ましい。従って、以下、本
発明をハロゲンが塩素の場合を代表例として説明する
が、本発明はハロゲンが臭素またはヨウ素である場合に
も適用できる。本発明の低ルチル型超微粒子酸化チタン
は、気相法で四塩化チタンを用いて製造したものである
にもかかわらず、粒子内部に塩素が殆ど存在しない。粒
子内部に残存する塩素は経時的に粒子内部から表面まで
拡散し基材を腐食、変質させることがあるが、水洗や乾
燥等の簡単な脱塩素処理では除去しにくい。そのため、
酸化チタン粒子内部に塩素が存在しないことが望まし
い。粒子表面と粒子内部の合計塩素量のうちに占める粒
子内部の塩素含有率については、酸化チタンから純水で
抽出される塩素（水抽出塩素と称する）と、酸化チタン
粒子に含まれる全塩素（全塩素と称する）の比率を指標
とし、下式（１）
Ｒ＝ＷＣＬ／ＴＣＬ×１００ ・・・・・・・・・・（１）
（式中、Ｒは表面塩素率（％）を表し、ＷＣＬは酸化チ
タンに含まれる水抽出塩素の含有量（質量％）を表し、
ＴＣＬは酸化チタンに含まれる全塩素の含有量（質量
％）を表す。）で表されるＲの値が高いほど酸化チタン
粒子内部の塩素含有率が少ないことを示す。本発明にお
ける酸化チタンについて、Ｒは８０％以上であることが
好ましく、更に好ましくは９０％以上である。BEST MODE FOR CARRYING OUT THE INVENTION As a titanium halide which is a raw material for the titanium oxide of the present invention, titanium chloride, which is easily industrially available, and titanium tetrachloride is particularly preferable. Therefore, although the present invention will be described below by taking the case where the halogen is chlorine as a typical example, the present invention can be applied to the case where the halogen is bromine or iodine. Although the low rutile type ultrafine particle titanium oxide of the present invention is manufactured by using titanium tetrachloride by a vapor phase method, chlorine hardly exists inside the particles. Chlorine remaining inside the particles may diffuse from the inside of the particles to the surface over time to corrode and deteriorate the base material, but it is difficult to remove it by simple dechlorination such as washing with water or drying. for that reason,
It is desirable that chlorine is not present inside the titanium oxide particles. Regarding the chlorine content inside the particles in the total amount of chlorine on the surface and inside the particles, the chlorine extracted from the titanium oxide with pure water (referred to as water-extracted chlorine) and the total chlorine contained in the titanium oxide particles ( The following formula (1) R = WCL / TCL × 100 (1) (wherein R represents the surface chlorine ratio (%)) , WCL represents the content (mass%) of water-extracted chlorine contained in titanium oxide,
TCL represents the total chlorine content (mass%) contained in titanium oxide. The higher the value of R represented by), the lower the chlorine content inside the titanium oxide particles. With respect to the titanium oxide in the present invention, R is preferably 80% or more, more preferably 90% or more.
【００２１】本発明の四塩化チタンを原料とする気相法
によって得られる超微粒子酸化チタンは、ルチル含有率
〔ルチル含有率は、Ｘ線回折におけるルチル型結晶に対
応するピーク高さ（Ｈｒと略する。）、ブルッカイト型
結晶に対応するピーク高さ（Ｈｂと略する。）及びアナ
ターゼ型結晶に対応するピーク高さ（Ｈａと略する。）
から算出した比率（＝１００×Ｈｒ／（Ｈｒ＋Ｈａ＋Ｈ
ｂ）をいう。〕が５％以下の超微粒子酸化チタン（以
下、低ルチル型の超微粒子酸化チタンと略称することが
ある。）であり、かつ、脱塩素工程の後のみならず、場
合によっては脱塩素工程の前でも、下記一般式（２）：
Ｃ≦６５０×ｅ0.02B ・・・・・・・・・・・・・・・（２）
で表される全塩素含有量を有する。式中、Ｃは全塩素含
有量（質量％）を示す。Ｃは、例えば、酸化チタンにフ
ッ酸水溶液を添加しマイクロウェーブで加熱溶解させた
液を、硝酸銀による電位差滴定法で測定し、酸化チタン
中の塩素の質量を得、これを用いた酸化チタンの質量で
除することにより得られる。ＢはＢＥＴ比表面積（ｍ2
／ｇ）を表し、その範囲は１０〜２００ｍ2／ｇであ
る。）で表される特性を有することを特徴とする。The ultrafine titanium oxide obtained by the vapor phase method using titanium tetrachloride as a raw material according to the present invention has a rutile content [a rutile content is a peak height (Hr and Hr) corresponding to a rutile type crystal in X-ray diffraction. Abbreviated), peak height corresponding to brookite type crystal (abbreviated as Hb) and peak height corresponding to anatase type crystal (abbreviated as Ha).
The ratio calculated from (= 100 × Hr / (Hr + Ha + H
b). ] Is 5% or less of ultrafine particle titanium oxide (hereinafter, may be abbreviated as low rutile type ultrafine particle titanium oxide), and not only after the dechlorination step but also in the dechlorination step in some cases. Even before, it has a total chlorine content represented by the following general formula (2): C ≦ 650 × e 0.02B (2) In the formula, C represents the total chlorine content (mass%). For C, for example, a hydrofluoric acid aqueous solution was added to titanium oxide and heated and dissolved in a microwave to measure the liquid by a potentiometric titration method with silver nitrate to obtain the mass of chlorine in titanium oxide. It is obtained by dividing by the mass. B is the BET specific surface area (m 2
/ G), and the range is 10 to 200 m 2 / g. ) Has a characteristic represented by.
【００２２】すなわち、本発明の低ルチル型の超微粒子
酸化チタンは、図１において上記一般式（２）の条件を
満足する全塩素含有量の少ない酸化チタンであり、かつ
上記式（１）のＲが大きい粒子内部の塩素含有率の小さ
い酸化チタン粒子である。従来の四塩化チタンを原料と
する気相法による超微粒子酸化チタンは、低ルチル型酸
化チタンであっても、ＢＥＴ比表面積と全塩素含有量と
の関係において図１に示したＣ＝６５０×ｅ0.02Bで表
される曲線の上部にプロットされる領域の特性を有して
いるものであり、さらにまた上記の粒子内部の塩素含有
率も大きい酸化チタン粒子であった。特に、比表面積の
大きい酸化チタンほど、脱塩素されにくく、塩素含有量
が指数関数的に増加する傾向がある。That is, the low rutile type ultrafine particle titanium oxide of the present invention is a titanium oxide having a small total chlorine content which satisfies the condition of the above general formula (2) in FIG. The titanium oxide particles have a small R content inside the particles having a large R. The conventional ultrafine particle titanium oxide prepared by the vapor phase method using titanium tetrachloride as a raw material, even if it is a low rutile type titanium oxide, has a relationship between the BET specific surface area and the total chlorine content of C = 650 × shown in FIG. e Titanium oxide particles having the characteristics of the region plotted above the curve represented by 0.02B and having a large chlorine content inside the above particles. In particular, titanium oxide having a larger specific surface area is less likely to be dechlorinated, and the chlorine content tends to exponentially increase.
【００２３】本発明の低ルチル型酸化チタンは、塩素含
有量とＢＥＴ比表面積との関係が一般式（２）の特性を
満足し、超微粒子であって、通常、ＢＥＴ比表面積の範
囲は１０〜２００ｍ2／ｇ、好ましくは４０〜２００ｍ2
／ｇ、更に好ましくは４５〜１２０ｍ2／ｇの範囲を有
するものである。The low rutile type titanium oxide of the present invention has a relationship between the chlorine content and the BET specific surface area that satisfies the characteristic of the general formula (2) and is an ultrafine particle, and the range of the BET specific surface area is usually 10 ~200m 2 / g, preferably 40~200m 2
/ G, more preferably 45 to 120 m 2 / g.
【００２４】また、本発明の低ルチル型の超微粒子酸化
チタンは、Ｆｅ、Ａｌ、Ｓｉ、Ｓの含有量が各１００質
量ｐｐｍ以下、好ましくは各０．１〜１００質量ｐｐ
ｍ、より好ましくは各０．１〜５０質量ｐｐｍ、更に好
ましくは各０．１〜１０質量ｐｐｍである。これらの不
純物濃度を０．１ｐｐｍ未満にするには、酸化チタンを
製造する原材料を高純度とし、また設備材質をより耐食
性の高いものを使用すること等が必要となる。本発明の
酸化チタンが通常用いられる用途では、各不純物を０．
１質量ｐｐｍ未満としない方が経済的に有利である。In the low rutile type ultrafine particle titanium oxide of the present invention, the content of Fe, Al, Si and S is each 100 mass ppm or less, preferably 0.1 to 100 mass pp.
m, more preferably 0.1 to 50 mass ppm each, further preferably 0.1 to 10 mass ppm each. In order to reduce the concentration of these impurities to less than 0.1 ppm, it is necessary to use a raw material for producing titanium oxide with high purity and use equipment having higher corrosion resistance. In the applications where the titanium oxide of the present invention is usually used, each impurity is added to 0.1
It is economically advantageous not to make it less than 1 mass ppm.
【００２５】本発明の低ルチル型酸化チタンは分散性が
高いことを特徴とする。本発明においては、分散性の指
標としてレーザー回折式粒度分布測定法を採用し粒度分
布を測定した。分散性の測定法には、「超微粒子ハンド
ブック」齋藤進六監修，フジ・テクノシステム，ｐ９
３，（１９９０）によると、沈降法、顕微鏡法、光散乱
法、直接計数法等があるが、このうち沈降法、直接計数
法は測定可能な粒径が数百ｎｍ以上であり、超微粒子の
分散性を測定するには不適である。また、顕微鏡法も対
象試料のサンプリングや試料の前処理によって測定値が
変動することもあり、好ましい測定法とはいえない。こ
れに対し、光散乱法は数ｎｍ〜数μｍの範囲で粒径を測
定することができ、超微粒子の測定に適している。粒度
分布の測定手順について以下に説明する。The low rutile type titanium oxide of the present invention is characterized by high dispersibility. In the present invention, the particle size distribution was measured by using a laser diffraction type particle size distribution measuring method as an index of dispersibility. For the method of measuring dispersibility, "Ultrafine particle handbook", supervised by Shinroku Saito, Fuji Techno System, p9
3, (1990), there are a sedimentation method, a microscope method, a light scattering method, a direct counting method and the like. Among them, the sedimentation method and the direct counting method have a measurable particle size of several hundreds nm or more, and are ultrafine particles. Is not suitable for measuring the dispersibility of In addition, the microscopic method is not a preferable measuring method because the measured value may change due to sampling of the target sample or pretreatment of the sample. On the other hand, the light scattering method can measure the particle size in the range of several nm to several μm, and is suitable for the measurement of ultrafine particles. The procedure for measuring the particle size distribution will be described below.
【００２６】酸化チタン０．０５ｇに純水５０ｍｌ及び
１０％ヘキサメタリン酸ソーダ水溶液１００μｌを加え
たスラリーに、３分間超音波照射（４６ＫＨｚ、６５
Ｗ）する。このスラリーをレーザー回折式粒度分布測定
装置（（株）島津製作所製ＳＡＬＤ−２０００Ｊ）にか
けて、粒度分布を測定する。このようにして測定された
粒度分布における９０％累積質量粒度分布径（以下、Ｄ
９０と略記することがある）の値が小さければ、親水性
溶媒に対して良好な分散性を示していると判断される。
５０％累積質量粒度分布径を分散性の指標とすることも
可能であるが、分散性の悪い凝集粒子を検知しにくく好
ましくない。本発明の超微粒子酸化チタンは、Ｄ９０が
２．５μｍ以下であることが好ましい。A slurry obtained by adding 50 ml of pure water and 100 μl of 10% aqueous sodium hexametaphosphate solution to 0.05 g of titanium oxide was subjected to ultrasonic irradiation for 3 minutes (46 KHz, 65
W) This slurry is applied to a laser diffraction particle size distribution analyzer (SALD-2000J manufactured by Shimadzu Corporation) to measure the particle size distribution. 90% cumulative mass particle size distribution diameter (hereinafter D
90) may be abbreviated as good).
Although it is possible to use the 50% cumulative mass particle size distribution diameter as an index of dispersibility, it is not preferable because it is difficult to detect aggregated particles having poor dispersibility. The D90 of the ultrafine titanium oxide particles of the present invention is preferably 2.5 μm or less.
【００２７】本発明の超微粒子状酸化チタンは、各種組
成物の原料、顔料または光触媒効果を利用した粒子成分
として含まれ、例えば、化粧料、紫外線遮蔽材、誘電体
またはシリコーンゴム、太陽電池等、様々な製品の原
料、添加剤として利用できる。The ultrafine particulate titanium oxide of the present invention is contained as a raw material for various compositions, a pigment or a particle component utilizing the photocatalytic effect, and is, for example, a cosmetic, an ultraviolet shielding material, a dielectric or silicone rubber, a solar cell and the like. It can be used as a raw material for various products and as an additive.
【００２８】次に製造方法について説明する。気相法に
よる一般的な酸化チタンの製造方法は公知であり、四塩
化チタンを酸素または水蒸気等の酸化性ガスを用いて、
約１，０００℃の反応条件下で酸化させると微粒子酸化
チタンが得られる。Next, the manufacturing method will be described. A general method for producing titanium oxide by a vapor phase method is known, and titanium tetrachloride is used with an oxidizing gas such as oxygen or water vapor.
Fine particles of titanium oxide are obtained by oxidation under a reaction condition of about 1,000 ° C.
【００２９】気相法において超微粒子の酸化チタンを得
るためには、粒子の成長時間（成長ゾーン）を短くしな
ければならない。すなわち、反応後速やかに冷却、希釈
等を行い、高温滞留時間を極力短くすることにより、焼
結等による粒成長を抑えることができる。高温滞留時間
の短縮はアナターゼからルチルへの熱転位を抑制するこ
とにも繋がり、アナターゼ含有率の高い粒子を得ること
ができる。In order to obtain ultrafine particles of titanium oxide in the vapor phase method, the particle growth time (growth zone) must be shortened. That is, grain growth due to sintering or the like can be suppressed by rapidly cooling and diluting after the reaction and shortening the high temperature residence time as much as possible. Shortening the high temperature residence time leads to suppression of thermal rearrangement from anatase to rutile, and particles having a high anatase content can be obtained.
【００３０】一般に、四塩化チタンを原料とする気相法
で得られる酸化チタンには、通常、０．１〜２質量％の
塩素が残存している。アナターゼ型酸化チタン表面に
は、塩素等が結合可能な点が１３個／ｎｍ2あり（前述
の清野学著「酸化チタン」）、この全ての結合点が塩素
化している場合、酸化チタン粒子表面に残存する塩素含
有量は理論上、下式（３）で表される。
Ｙ＝０．０７７×Ａ ・・・・（３）
（式中、Ｙは酸化チタン粒子表面に残存する塩素含有量
（質量％）を示し、Ａは比表面積（ｍ2／ｇ）を示
す。）
例えば、１００ｍ2／ｇの比表面積を有する酸化チタン
粒子表面に残存する塩素含有量は、前記式（３）によれ
ば、約８質量％となる。In general, 0.1 to 2% by mass of chlorine generally remains in titanium oxide obtained by a vapor phase method using titanium tetrachloride as a raw material. On the anatase type titanium oxide surface, there are 13 points / nm 2 that can bind chlorine and the like ("Titanium oxide" written by Manabu Seino mentioned above). If all of these points are chlorinated, the titanium oxide particle surface The residual chlorine content is theoretically expressed by the following formula (3). Y = 0.077 × A (3) (In the formula, Y represents the chlorine content (mass%) remaining on the surface of the titanium oxide particles, and A represents the specific surface area (m 2 / g). ) For example, the chlorine content remaining on the surface of titanium oxide particles having a specific surface area of 100 m 2 / g is about 8 mass% according to the above formula (3).
【００３１】実際は、反応で塩素と酸化性ガスが置換す
ること、また酸化チタン粒子表面と気相の塩素濃度差に
よって塩素が平衡移動することにより、酸化チタンの塩
素含有量は前記式（３）で得られる値よりも若干低くな
る可能性があるが、反応での高温滞留時間の短縮は、四
塩化チタンの酸化反応を完結させず、一部が塩素化され
たままの酸化チタンを増加させることになると考えられ
る。また、残存塩素が酸化チタン粒子内部に取り残され
ると粒子内部の塩素量を増やすことにもなるため、塩素
除去に要する加熱処理が高温、長時間化し、比表面積の
低下を生じることとなる。従って、従来、気相法によっ
て得られる超微粒子は、アナターゼ含有率は高いものの
塩素含有量が高い、あるいは、塩素含有量は低いがアナ
ターゼ含有率が低いというものであった。Actually, the chlorine content of titanium oxide is determined by the above formula (3) by the substitution of chlorine and oxidizing gas in the reaction and the equilibrium movement of chlorine due to the difference in chlorine concentration between the surface of titanium oxide particles and the gas phase. Although it may be slightly lower than the value obtained in, the reduction of the high temperature residence time in the reaction does not complete the oxidation reaction of titanium tetrachloride and increases the titanium oxide partially chlorinated. I think that will be the case. Further, if residual chlorine is left inside the titanium oxide particles, the amount of chlorine inside the particles also increases, so that the heat treatment required for chlorine removal becomes high temperature and long time, and the specific surface area decreases. Therefore, conventionally, the ultrafine particles obtained by the vapor phase method have a high anatase content but a high chlorine content, or a low chlorine content but a low anatase content.
【００３２】本発明では、四塩化チタンを含むガスと酸
化性ガスとを反応（高温酸化）することにより酸化チタ
ンを製造する気相法において、６００℃以上１，１００
℃未満に加熱した四塩化チタンを含有するガス及び６０
０℃以上１，１００℃未満に加熱した酸化性ガスをそれ
ぞれ反応管に供給し、反応させて得られた酸化チタンを
８００℃以上１，１００℃未満の高温度条件で０．１秒
以下の時間、反応管内に滞留させることにより、ＢＥＴ
比表面積と塩素含有量との関係において全塩素含有量、
特に粒子内部の塩素含有量が低い低ルチル型超微粒子酸
化チタンが得られ、これを脱塩素処理することによりさ
らに全塩素含有量が低くかつ粒子内部の塩素含有量も低
い低ルチル型超微粒子酸化チタンが得られることを見出
した。ここで、脱塩素には乾式法と湿式法がある。乾式
脱塩素法は、例えば、円筒形回転式加熱炉、熱風循環式
加熱炉、流動乾燥炉、撹拌乾燥炉等の加熱装置を用いて
酸化チタンを加熱し、塩素を除去する方法がある。尚、
本発明は、必ずしもこれら加熱装置に限定されるもので
はない。また、湿式脱塩素法は、例えば、酸化チタンを
純水に懸濁させ、液相に移行した塩素を系外に分離する
方法がある。塩素を系外に分離した後、得られた酸化チ
タンを乾燥しても良い。In the present invention, in a gas phase method for producing titanium oxide by reacting a gas containing titanium tetrachloride with an oxidizing gas (high temperature oxidation), 600 ° C. or more and 1,100
Gas containing titanium tetrachloride heated to less than 60 ° C and 60
Oxidizing gas heated to 0 ° C. or higher and lower than 1,100 ° C. is supplied to the reaction tubes, respectively, and titanium oxide obtained by the reaction is heated at 800 ° C. or higher and lower than 1,100 ° C. for 0.1 second or less BET by staying in the reaction tube for a certain time
Total chlorine content in relation to specific surface area and chlorine content,
In particular, low rutile ultrafine particle titanium oxide with a low chlorine content inside the particle was obtained. By dechlorinating this, low rutile ultrafine particle oxidation with a low total chlorine content and a low chlorine content inside the particle was also obtained. It has been found that titanium can be obtained. Here, dechlorination includes a dry method and a wet method. As the dry dechlorination method, for example, there is a method of removing titanium by heating titanium oxide using a heating device such as a cylindrical rotary heating furnace, a hot air circulation heating furnace, a fluidized drying furnace, and a stirring drying furnace. still,
The present invention is not necessarily limited to these heating devices. Further, the wet dechlorination method includes, for example, a method in which titanium oxide is suspended in pure water and chlorine that has moved to a liquid phase is separated from the system. After separating chlorine out of the system, the titanium oxide obtained may be dried.
【００３３】四塩化チタン含有ガスあるいは酸化性ガス
を導入する反応管内の温度は８００℃以上１，１００℃
未満が好ましく、更に好ましくは９００℃以上１，００
０℃未満である。反応管内温度を高くすることによっ
て、混合と同時に反応は完結するので均一核発生が増進
され、かつ、反応（ＣＶＤ）ゾーンを小さくすることが
できる。反応管内温度が８００℃より低いと、アナター
ゼ含有率の高い酸化チタンが得られやすいものの、反応
が不充分で酸化チタン粒子内部に塩素が残存する。反応
管内温度が１，１００℃以上になるとルチル転移や粒子
成長が進行し、低ルチル型、超微粒子が得られない。The temperature in the reaction tube for introducing the titanium tetrachloride-containing gas or oxidizing gas is 800 ° C. or higher and 1,100 ° C.
Is preferably less than 900 ° C., more preferably 900 ° C.
It is less than 0 ° C. By increasing the temperature in the reaction tube, the reaction is completed at the same time as the mixing, so that uniform nucleation is promoted and the reaction (CVD) zone can be made small. When the temperature in the reaction tube is lower than 800 ° C., titanium oxide having a high anatase content is likely to be obtained, but the reaction is insufficient and chlorine remains inside the titanium oxide particles. When the temperature in the reaction tube is 1,100 ° C. or higher, rutile transition and particle growth proceed, and low rutile type and ultrafine particles cannot be obtained.
【００３４】一方、原料ガスが反応管に導入され反応が
進行すると、本反応が発熱反応である為、反応温度が
１，１００℃を越える反応ゾーンが存在する。装置放熱
は多少あるものの、急冷を施さないかぎり酸化チタン粒
子はどんどん成長し、かつ、結晶型がルチルに転移して
しまう。そこで、本発明においては８００℃以上１，１
００℃未満の高温滞留時間を０．１秒以下、好ましくは
０．００５〜０．１秒、特に好ましくは０．０１〜０．
０５秒の範囲にする。高温滞留時間が０．１秒を越える
と、ルチルへの転移や粒子の焼結が進行するので好まし
くない。高温滞留時間が０．００５秒未満では、四塩化
チタンの酸化反応時間も短くなるため、四塩化チタンに
比べ十分に過剰な酸素量を用いるなど酸化を行い易い条
件下で行う必要がある。酸化が不十分では粒子内部の残
存塩素量増加につながる。On the other hand, when the raw material gas is introduced into the reaction tube and the reaction proceeds, this reaction is an exothermic reaction, so that there is a reaction zone in which the reaction temperature exceeds 1,100 ° C. Although there is some heat dissipation from the device, the titanium oxide particles grow steadily and the crystal form changes to rutile unless rapid cooling is applied. Therefore, in the present invention, 800 ° C or higher 1,1
A high temperature residence time of less than 00 ° C is 0.1 seconds or less, preferably 0.005 to 0.1 seconds, particularly preferably 0.01 to 0.
Set to the range of 05 seconds. If the high temperature residence time exceeds 0.1 seconds, the transition to rutile and the sintering of particles proceed, which is not preferable. When the high temperature residence time is less than 0.005 seconds, the oxidation reaction time of titanium tetrachloride is shortened. Therefore, it is necessary to carry out the conditions under which oxidation is easy, such as using a sufficiently excess amount of oxygen as compared with titanium tetrachloride. Insufficient oxidation leads to an increase in the amount of residual chlorine inside the particles.
【００３５】急冷の手段としては、例えば、反応混合物
に多量の冷却空気や窒素等のガスを導入する方法、ある
いは水を噴霧する方法等が採用される。As means for quenching, for example, a method of introducing a large amount of cooling air or a gas such as nitrogen into the reaction mixture, or a method of spraying water is adopted.
【００３６】反応管内の温度を前記８００℃以上１，１
００℃未満に制御することで粒子内部の塩素含有量が低
い超微粒子を得ることができ、また、高温滞留時間を
０．１秒以下に制御することでルチル転移及び粒成長を
抑制することができる。The temperature in the reaction tube is 800 ° C. or higher 1,1
By controlling the temperature below 00 ° C, it is possible to obtain ultrafine particles having a low chlorine content inside the particles, and by controlling the high temperature residence time at 0.1 seconds or less, it is possible to suppress rutile transition and grain growth. it can.
【００３７】反応管内の温度を前記８００℃以上１，１
００℃未満にするためには、原料ガスの加熱温度を６０
０℃以上１，１００℃以下に調整することが好ましい。
加熱された原料ガスは反応管内で反応し発熱するが、原
料ガス温度が６００℃未満であると、反応管内の温度は
８００℃以上になりにくい。また、原料ガス温度が１，
１００℃以上であると装置放熱はあるものの、反応管内
の温度は１，１００℃を越えやすくなる。The temperature in the reaction tube is 800 ° C. or higher 1,1
In order to keep the temperature below 00 ° C, the heating temperature of the source gas is 60
It is preferable to adjust the temperature to 0 ° C or higher and 1100 ° C or lower.
The heated raw material gas reacts in the reaction tube to generate heat, but when the temperature of the raw material gas is lower than 600 ° C., the temperature in the reaction tube is unlikely to reach 800 ° C. or higher. In addition, the source gas temperature is 1,
If the temperature is 100 ° C. or higher, the heat is radiated from the apparatus, but the temperature in the reaction tube easily exceeds 1,100 ° C.
【００３８】四塩化チタンを含む原料ガス組成は、四塩
化チタンガス１モルに対し、不活性ガス０．１〜２０モ
ルであることが好ましく、さらに好ましくは４〜２０モ
ルである。不活性ガスが前記範囲より少ない場合、反応
ゾーンにおける酸化チタン粒子密度が高まり、凝集、焼
結しやすくなるため、超微粒子酸化チタンが得られにく
い。不活性ガスが前記範囲よりも多い場合、反応性が低
下し、酸化チタンとしての回収率が低下する。The composition of the raw material gas containing titanium tetrachloride is preferably 0.1 to 20 mol, more preferably 4 to 20 mol, based on 1 mol of titanium tetrachloride gas. If the amount of the inert gas is less than the above range, the density of titanium oxide particles in the reaction zone increases, and the particles easily aggregate and sinter, so that it is difficult to obtain ultrafine particle titanium oxide. When the amount of the inert gas is more than the above range, the reactivity is lowered and the recovery rate as titanium oxide is lowered.
【００３９】四塩化チタンを含む原料ガスと反応させる
酸素ガス量は、四塩化チタン１モルに対し１〜３０モル
であることが好ましい。さらに好ましくは５〜３０モル
である。酸素ガス量を増やすと、核発生数が増加し超微
粒子は得られやすくなるが、３０モルを越えても核発生
数を増加させる効果はほとんど無い。酸素ガス量が３０
モルを越えても酸化チタンの特性に影響は無いが、経済
的な観点から上限が設定される。一方、四塩化チタンに
対し酸素ガス量が不足すると、酸素欠陥の多い酸化チタ
ンとなり着色してしまう。尚、酸化性ガスには、酸素の
他に水蒸気が含まれていても良い。酸化性ガスは、例え
ば、酸素、水蒸気を含む酸素、空気、これらの酸化性ガ
スに不活性ガス（窒素、アルゴンなど）を混合したガス
がいずれも使用できるが、反応温度の制御しやすいこと
から水蒸気を含む酸素が好ましい。The amount of oxygen gas reacted with the raw material gas containing titanium tetrachloride is preferably 1 to 30 mol per mol of titanium tetrachloride. It is more preferably 5 to 30 mol. When the amount of oxygen gas is increased, the number of generated nuclei increases and ultrafine particles are easily obtained, but even if it exceeds 30 mol, there is almost no effect of increasing the number of generated nuclei. The amount of oxygen gas is 30
Although the properties of titanium oxide are not affected if the amount exceeds the upper limit, the upper limit is set from the economical point of view. On the other hand, if the amount of oxygen gas is insufficient with respect to titanium tetrachloride, titanium oxide with many oxygen defects will be colored. The oxidizing gas may include water vapor in addition to oxygen. As the oxidizing gas, for example, oxygen, oxygen containing water vapor, air, or a gas obtained by mixing these oxidizing gases with an inert gas (nitrogen, argon, etc.) can be used, but it is easy to control the reaction temperature. Oxygen containing water vapor is preferred.
【００４０】酸化チタンの加熱による脱塩素は、水と酸
化チタンとの質量比（＝水蒸気の質量／酸化チタンの質
量，以下同様）が０．０１以上になるように酸化チタン
粉末に水蒸気を接触させながら加熱温度２００℃以上５
００℃以下で行うことが好ましい。更に好ましくは水と
酸化チタンの質量比は０．０４以上、加熱温度は２５０
℃以上４５０℃以下である。加熱温度が５００℃を越え
ると酸化チタン粒子の焼結が進み、粒成長が生じる。加
熱温度が２００℃を下回ると脱塩素の効率が極端に低下
する。脱塩素は、酸化チタン表面の塩素が粒子近傍の水
あるいは隣接する粒子の表面水酸基と置換反応すること
により進行して行く。酸化チタン粒子表面の塩素が、水
と置換された場合には粒成長せずに脱塩素化されるが、
隣接する粒子の表面水酸基と置換された場合は脱塩素と
同時に粒成長することとなる。特に比表面積の大きい酸
化チタンほど隣接する粒子表面水酸基と置換反応する確
率が高くなるため、粒成長しやすい。すなわち、粒成長
を抑制しつつ脱塩素化を図るためには水と酸化チタンの
質量比も重要であり、水と酸化チタンの質量比が０．０
１以上であれば粒成長を抑制する効果が認められる。For dechlorination by heating titanium oxide, steam is contacted with titanium oxide powder so that the mass ratio of water to titanium oxide (= mass of steam / mass of titanium oxide, the same applies hereinafter) is 0.01 or more. Heating temperature 200 ℃ or more 5
It is preferably carried out at a temperature of 00 ° C or lower. More preferably, the mass ratio of water to titanium oxide is 0.04 or more, and the heating temperature is 250.
The temperature is from ℃ to 450 ℃. When the heating temperature exceeds 500 ° C., the titanium oxide particles are sintered and the particles grow. If the heating temperature is lower than 200 ° C, the efficiency of dechlorination is extremely reduced. Dechlorination proceeds by chlorine substitution on the surface of titanium oxide with water in the vicinity of particles or surface hydroxyl groups of adjacent particles. Chlorine on the surface of titanium oxide particles is dechlorinated without grain growth when replaced with water,
When the surface hydroxyl groups of adjacent particles are substituted, the particles grow simultaneously with dechlorination. In particular, titanium oxide having a larger specific surface area has a higher probability of undergoing a substitution reaction with a hydroxyl group on the surface of an adjacent particle, and thus is more likely to grow. That is, the mass ratio of water and titanium oxide is important in order to achieve dechlorination while suppressing grain growth, and the mass ratio of water and titanium oxide is 0.0
If it is 1 or more, the effect of suppressing grain growth is recognized.
【００４１】酸化チタンと接触させる水蒸気は、酸化チ
タンから分離した塩素を効率良く系外に移動させる役割
を有するガスと混合して使用することが好ましい。この
ようなガスとして、例えば、空気が挙げられる。空気を
用いる場合、水蒸気は、空気に０．１容量％以上含まれ
ることが好ましく、更に好ましくは５容量％以上、特に
好ましくは１０容量％以上である。水蒸気を含んだ空気
は２００℃以上１，０００℃以下に加熱しておくことが
好ましい。The water vapor which is brought into contact with the titanium oxide is preferably used as a mixture with a gas having a role of efficiently moving chlorine separated from the titanium oxide out of the system. Examples of such a gas include air. When using air, the water vapor content in the air is preferably 0.1% by volume or more, more preferably 5% by volume or more, and particularly preferably 10% by volume or more. Air containing water vapor is preferably heated to 200 ° C. or higher and 1,000 ° C. or lower.
【００４２】本発明による低ルチル型超微粒子酸化チタ
ンは粒子内部に塩素が殆ど存在しないため、湿式で低塩
素化することも可能である。湿式脱塩素方法には、例え
ば、酸化チタンを純水に懸濁させ、液相に移行した塩素
を限外ろ過膜、逆浸透膜、フィルタープレス等によって
系外に分離する方法が挙げられる。このようにして製造
される本発明のＢＥＴ比表面積とハロゲン含有量との関
係において全ハロゲン含有量および粒子内部のハロゲン
含有量の低い低ルチル型超微粒子酸化チタンは、好まし
くは粒子表面のハロゲンをより完全に脱ハロゲンするこ
とで、ＢＥＴ比表面積との関係において全ハロゲン含有
量が極めて低い低ルチル型超微粒子酸化チタンを得るこ
とができる。従って、本発明の低ルチル型超微粒子酸化
チタンは、上記の如く、ルチル含有率が５％以下、ＢＥ
Ｔ一点法で測定した比表面積が１０〜２００ｍ2／ｇ、
レーザー回折式粒度分析計によって測定される９０％累
積質量粒度分布径が２．５μｍ以下の酸化チタン粒子で
あり、かつ、ＢＥＴ一点法で測定した酸化チタンの比表
面積をＢ（ｍ2／ｇ）、酸化チタン粒子内部のハロゲン
含有量をＣi（質量ｐｐｍ）としたとき、粒子内部に含
まれるハロゲン量が０≦Ｃi≦６５０ｋｅ0.02B（ｋは
０．２０）、好ましくは０＜Ｃi≦６５０ｋｅ0.02B（ｋ
は０．２０）、より好ましくは１０＜Ｃi≦６５０ｋｅ
0.02B（ｋは０．１５）で示されることを特徴とする。Since the low rutile type ultrafine titanium oxide particles according to the present invention have almost no chlorine inside the particles, it is possible to reduce the chlorine content by a wet method. Examples of the wet dechlorination method include a method in which titanium oxide is suspended in pure water and chlorine transferred to the liquid phase is separated from the system by an ultrafiltration membrane, a reverse osmosis membrane, a filter press or the like. The low rutile type ultrafine particle titanium oxide having a low total halogen content and a low halogen content in the particles in the relationship between the BET specific surface area and the halogen content of the present invention produced in this manner preferably contains halogen on the particle surface. More complete dehalogenation makes it possible to obtain low rutile ultrafine titanium oxide having a very low total halogen content in relation to the BET specific surface area. Therefore, the low rutile type ultrafine particle titanium oxide of the present invention has a rutile content of 5% or less as described above.
The specific surface area measured by the T-point method is 10 to 200 m 2 / g,
90% cumulative mass particle size distribution diameter measured by a laser diffraction type particle size analyzer is 2.5 μm or less, and the specific surface area of titanium oxide measured by the BET single point method is B (m 2 / g). When the halogen content in the titanium oxide particles is C i (mass ppm), the amount of halogen contained in the particles is 0 ≦ C i ≦ 650 ke 0.02 B (k is 0.20), preferably 0 <C i ≦ 650ke 0.02B (k
Is 0.20), more preferably 10 <C i ≦ 650 ke
It is characterized by being indicated by 0.02B (k is 0.15).
【００４３】[0043]
【実施例】以下、実施例及び比較例にて具体的に説明す
るが、本発明はこれらに何ら限定されるものではない。EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
【００４４】実施例１：１１．８Ｎｍ3／ｈｒ（Ｎは標
準状態を意味する。以下同じ。）のガス状四塩化チタン
を８Ｎｍ3／ｈｒの窒素ガスで希釈した四塩化チタン希
釈ガスを９００℃に予熱し、８Ｎｍ3／ｈｒの酸素と３
２Ｎｍ3／ｈｒ水蒸気を混合した酸化性ガスを８００℃
に予熱し、これらの原料ガスを石英ガラス製反応器に導
入した。８００℃以上１，１００℃未満の高温滞留時間
を０．１秒となるように冷却空気を反応管に導入後、ポ
リテトラフルオロエチレン製バグフィルターにて超微粒
子状酸化チタン粉末を捕集した。Example 1: 11.8 Nm 3 / hr (N means a standard state; the same applies hereinafter) of gaseous titanium tetrachloride was diluted with 8 Nm 3 / hr of nitrogen gas to give titanium tetrachloride diluted gas of 900. Preheat to ℃, 8Nm 3 / hr oxygen and 3
Oxidizing gas mixed with 2Nm 3 / hr steam is 800 ° C
Were preheated, and these raw material gases were introduced into a quartz glass reactor. Cooling air was introduced into the reaction tube so that the high-temperature residence time at 800 ° C. or higher and lower than 1,100 ° C. was 0.1 second, and then ultrafine titanium oxide powder was collected by a polytetrafluoroethylene bag filter.
【００４５】得られた酸化チタンを円筒形回転式加熱炉
に通し、水と酸化チタンの質量比０．０２、加熱温度４
５０℃で脱塩素した。その後、得られた酸化チタンは、
ＢＥＴ比表面積が２２ｍ2／ｇ、ルチル含有比率（ルチ
ル含有率ともいう。）が１％、水抽出塩素含有量が９０
０質量ｐｐｍ、全塩素含有量が１，０００質量ｐｐｍで
あった。但し、ＢＥＴ比表面積は、島津製作所製比表面
積測定装置（機種はフローソーブＩＩ，２３００）で測
定し、ルチル含有比率はＸ線回折におけるルチル型結晶
に対応するピーク高さ（Ｈｒと略する。）、ブルッカイ
ト型結晶に対応するピーク高さ（Ｈｂと略する。）とア
ナターゼ型結晶に対応するピーク高さ（Ｈａと略す
る。）から算出した比率（＝１００×Ｈｒ／（Ｈｒ＋Ｈ
ａ＋Ｈｂ））である。式（１）に水抽出塩素含有量 ９
００質量ｐｐｍ、全塩素含有量 １，０００質量ｐｐｍ
を代入して算出される表面塩素率は８０％よりも高く、
全塩素含有量は、式（２）に比表面積２２ｍ2／ｇを代
入して算出される値よりも小さな数値を示した。The obtained titanium oxide was passed through a cylindrical rotary heating furnace, and the mass ratio of water to titanium oxide was 0.02 and the heating temperature was 4
It was dechlorinated at 50 ° C. Then, the obtained titanium oxide,
BET specific surface area is 22 m 2 / g, rutile content ratio (also referred to as rutile content ratio) is 1%, water extracted chlorine content is 90.
The content was 0 mass ppm and the total chlorine content was 1,000 mass ppm. However, the BET specific surface area is measured by a Shimadzu specific surface area measuring device (model: Flowsorb II, 2300), and the rutile content ratio is the peak height (abbreviated as Hr) corresponding to the rutile type crystal in X-ray diffraction. , A ratio calculated from the peak height (abbreviated as Hb) corresponding to the brookite type crystal and the peak height (abbreviated as Ha) corresponding to the anatase type crystal (= 100 × Hr / (Hr + H
a + Hb)). The water extracted chlorine content in the formula (1) is 9
00 mass ppm, total chlorine content 1,000 mass ppm
The surface chlorine rate calculated by substituting is higher than 80%,
The total chlorine content showed a numerical value smaller than the value calculated by substituting the specific surface area of 22 m 2 / g into the formula (2).
【００４６】また、ここで得られた酸化チタン粉末の粒
度分布について、レーザー回折式粒度分布測定法で９０
％累積質量粒度分布径Ｄ９０を測定した結果、１．１μ
ｍであった。ルチル化率、ＢＥＴ比表面積、全塩素含有
量、表面塩素率、Ｄ９０、及び、Ｆｅ、Ａｌ、Ｓｉ、Ｓ
の分析結果を表１に示す。The particle size distribution of the titanium oxide powder obtained here was measured by a laser diffraction type particle size distribution measuring method.
As a result of measuring% cumulative mass particle size distribution diameter D90, 1.1 μ
It was m. Rutile ratio, BET specific surface area, total chlorine content, surface chlorine ratio, D90, and Fe, Al, Si, S
Table 1 shows the results of the analysis.
【００４７】実施例２：５．９Ｎｍ3／ｈｒのガス状四
塩化チタンを３０Ｎｍ3／ｈｒの窒素ガスで希釈した四
塩化チタン希釈ガスを１，０００℃に予熱し、４Ｎｍ3
／ｈｒの酸素と１６Ｎｍ3／ｈｒの水蒸気を混合した酸
化性ガスを１，０００℃に予熱し、これらの原料ガスを
石英ガラス製反応器に導入した。８００℃以上１，１０
０℃未満の高温滞留時間を０．０３秒となるように冷却
空気を反応管に導入後、ポリテトラフルオロエチレン製
バグフィルターにて超微粒子状酸化チタン粉末を捕集し
た。[0047] Example 2: 5.9Nm 3 / gaseous titanium tetrachloride hr preheated diluted titanium tetrachloride diluted gas 1,000 ° C. with nitrogen gas at 30Nm 3 / hr, 4Nm 3
/ Hr gas and 16Nm 3 / hr water vapor were mixed to preheat an oxidizing gas to 1,000 ° C., and these raw material gases were introduced into a quartz glass reactor. 800 ° C or higher 1,10
Cooling air was introduced into the reaction tube so that the high temperature residence time below 0 ° C. was 0.03 seconds, and then ultrafine particulate titanium oxide powder was collected by a polytetrafluoroethylene bag filter.
【００４８】得られた酸化チタンを熱風循環加熱炉に入
れ、水と酸化チタン質量比０．０４、加熱温度４５０℃
で脱塩素した。こうして得られた酸化チタンは、ＢＥＴ
比表面積が６５ｍ2／ｇ、ルチル含有率が３％、水抽出
塩素含有量が９００質量ｐｐｍ、全塩素含有量が１，１
００質量ｐｐｍであった。式（１）に水抽出塩素含有量
９００質量ｐｐｍ、全塩素含有量 １，１００質量ｐ
ｐｍを代入して算出される表面塩素率は８０％よりも高
く、全塩素含有量は、式（２）に比表面積６５ｍ2／ｇ
を代入して算出される値よりも小さな数値を示した。こ
の粉末のレーザー回折式粒度分布測定法にて測定した粒
度分布における９０％累積質量粒度分布径Ｄ９０は１．
９μｍであった。ルチル化率、ＢＥＴ比表面積、全塩素
含有量、表面塩素率、Ｄ９０、及び、Ｆｅ、Ａｌ、Ｓ
ｉ、Ｓの分析結果を表１に示す。The obtained titanium oxide was put into a hot air circulation heating furnace, and the mass ratio of water to titanium oxide was 0.04, and the heating temperature was 450 ° C.
Dechlorinated in. The titanium oxide thus obtained is BET
Specific surface area 65 m 2 / g, rutile content 3%, water extracted chlorine content 900 mass ppm, total chlorine content 1,1
It was 00 mass ppm. In formula (1), water-extracting chlorine content 900 mass ppm, total chlorine content 1,100 mass p
The surface chlorine rate calculated by substituting pm is higher than 80%, and the total chlorine content is 65 m 2 / g of the specific surface area in the formula (2).
A numerical value smaller than the value calculated by substituting is shown. The 90% cumulative mass particle size distribution diameter D90 in the particle size distribution of this powder measured by the laser diffraction type particle size distribution measurement method is 1.
It was 9 μm. Rutile ratio, BET specific surface area, total chlorine content, surface chlorine ratio, D90, and Fe, Al, S
Table 1 shows the analysis results of i and S.
【００４９】実施例３：４．７Ｎｍ3／ｈｒのガス状四
塩化チタンを３６Ｎｍ3／ｈｒの窒素ガスで希釈した四
塩化チタン希釈ガスを１，０００℃に予熱し、３６Ｎｍ
3／ｈｒの空気と２５Ｎｍ3／ｈｒの水蒸気を混合した酸
化性ガスを１，０００℃に予熱し、これらの原料ガスを
石英ガラス製反応器に導入した。８００℃以上１，１０
０℃未満の高温滞留時間を０．０２秒となるように冷却
空気を反応管に導入後、ポリテトラフルオロエチレン製
バグフィルターにて超微粒子状酸化チタン粉末を捕集し
た。Example 3: 4.7 Nm 3 / hr of gaseous titanium tetrachloride was diluted with 36 Nm 3 / hr of nitrogen gas, and a titanium tetrachloride diluent gas was preheated to 1,000 ° C. to obtain 36 Nm.
3 / hr of air and 25 Nm 3 / hr of oxidizing gas steam mixed with the preheated to 1,000 ° C., and the these raw material gases were introduced into a quartz glass reactor. 800 ° C or higher 1,10
Cooling air was introduced into the reaction tube so that the residence time at high temperature of less than 0 ° C was 0.02 seconds, and then ultrafine particulate titanium oxide powder was collected by a polytetrafluoroethylene bag filter.
【００５０】得られた酸化チタンを熱風循環加熱炉に入
れ、水と酸化チタン質量比０．０６、加熱温度３５０℃
で脱塩素した。こうして得られた酸化チタンは、ＢＥＴ
比表面積が９７ｍ2／ｇ、ルチル含有率が１％、水抽出
塩素含有率が１，８００質量ｐｐｍ、全塩素含有率が
２，０００質量ｐｐｍであった。式（１）に水抽出塩素
含有量 １，８００質量ｐｐｍ、全塩素含有量 ２，０
００質量ｐｐｍを代入して算出される表面塩素率は８０
％よりも高く、全塩素含有率は、式（２）に比表面積９
７ｍ2／ｇを代入して算出される値よりも小さな数値を
示した。この粉末のレーザー回折式粒度分布測定法にて
測定した粒度分布における９０％累積質量粒度分布径Ｄ
９０は２．２μｍであった。ルチル化率、ＢＥＴ比表面
積、全塩素含有量、表面塩素率、Ｄ９０、及び、Ｆｅ、
Ａｌ、Ｓｉ、Ｓの分析結果を表１に示す。The obtained titanium oxide was placed in a hot air circulation heating furnace, and the mass ratio of water to titanium oxide was 0.06, and the heating temperature was 350 ° C.
Dechlorinated in. The titanium oxide thus obtained is BET
The specific surface area was 97 m 2 / g, the rutile content was 1%, the water extracted chlorine content was 1800 mass ppm, and the total chlorine content was 2,000 mass ppm. In the formula (1), the water-extracting chlorine content is 1,800 mass ppm, the total chlorine content is 2,0
The surface chlorine rate calculated by substituting 00 mass ppm is 80
%, The total chlorine content is 9
The value is smaller than the value calculated by substituting 7 m 2 / g. 90% cumulative mass particle size distribution diameter D in the particle size distribution of this powder measured by the laser diffraction type particle size distribution measurement method
90 was 2.2 μm. Rutile ratio, BET specific surface area, total chlorine content, surface chlorine ratio, D90, and Fe,
Table 1 shows the analysis results of Al, Si, and S.
【００５１】比較例１：１１．８Ｎｍ3／ｈｒのガス状
四塩化チタンを８Ｎｍ3／ｈｒの窒素ガスで希釈した四
塩化チタン希釈ガスを９００℃に予熱し、８Ｎｍ3／ｈ
ｒの酸素と３２Ｎｍ3／ｈｒ水蒸気を混合した酸化性ガ
スを８００℃に予熱し、これらの原料ガスを石英ガラス
製反応器に導入した。８００℃以上１，１００℃未満の
高温滞留時間を０．２秒となるように冷却空気を反応管
に導入後、ポリテトラフルオロエチレン製バグフィルタ
ーにて超微粒子状酸化チタン粉末粉を捕集した。Comparative Example 1: 11.8 Nm 3 / hr of gaseous titanium tetrachloride was diluted with 8 Nm 3 / hr of nitrogen gas, and a titanium tetrachloride diluent gas was preheated to 900 ° C. to obtain 8 Nm 3 / h.
An oxidizing gas in which r of oxygen and 32 Nm 3 / hr of steam were mixed was preheated to 800 ° C., and these raw material gases were introduced into a quartz glass reactor. After introducing cooling air into the reaction tube so that the high-temperature residence time of 800 ° C. or higher and lower than 1,100 ° C. was 0.2 seconds, ultrafine particulate titanium oxide powder was collected by a polytetrafluoroethylene bag filter. .
【００５２】得られた酸化チタンを円筒形回転式加熱炉
に通し、水と酸化チタン質量比０．０２、加熱温度４５
０℃で脱塩素した。こうして得られた酸化チタンは、Ｂ
ＥＴ比表面積が１９ｍ2／ｇ、ルチル含有比率が１１
％、水抽出塩素含有量が３００質量ｐｐｍ、全塩素含有
量が３００質量ｐｐｍであった。式（１）に水抽出塩素
含有率 ３００質量ｐｐｍ、全塩素含有率 ３００質量
ｐｐｍを代入して算出される表面塩素率は８０％よりも
高く、全塩素含有率は、式（２）に比表面積１９ｍ2／
ｇを代入して算出される値よりも小さな数値を示した。
この粉末のレーザー回折式粒度分布測定法にて測定した
粒度分布における９０％累積質量粒度分布径Ｄ９０は
０．８μｍであった。ルチル化率、ＢＥＴ比表面積、全
塩素含有量、表面塩素率、Ｄ９０、及び、Ｆｅ、Ａｌ、
Ｓｉ、Ｓの分析結果を表１に示す。The obtained titanium oxide was passed through a cylindrical rotary heating furnace, and the mass ratio of water to titanium oxide was 0.02, and the heating temperature was 45.
Dechlorinated at 0 ° C. The titanium oxide thus obtained is B
ET specific surface area of 19 m 2 / g, rutile content ratio of 11
%, The water-extracted chlorine content was 300 mass ppm, and the total chlorine content was 300 mass ppm. The surface chlorine rate calculated by substituting the water extracted chlorine content rate of 300 mass ppm and the total chlorine content rate of 300 mass ppm into the formula (1) is higher than 80%, and the total chlorine content ratio is higher than that of the formula (2). Surface area 19m 2 /
A numerical value smaller than the value calculated by substituting g is shown.
The 90% cumulative mass particle size distribution diameter D90 in the particle size distribution of this powder measured by a laser diffraction type particle size distribution measuring method was 0.8 μm. Rutile ratio, BET specific surface area, total chlorine content, surface chlorine ratio, D90, Fe, Al,
Table 1 shows the analysis results of Si and S.
【００５３】比較例２：４．７Ｎｍ3／ｈｒのガス状四
塩化チタンを３６Ｎｍ3／ｈｒの窒素ガスで希釈した四
塩化チタン希釈ガスを８００℃に予熱し、３６Ｎｍ3／
ｈｒの空気と２５Ｎｍ3／ｈｒの水蒸気を混合した酸化
性ガスを８００℃に予熱し、これらの原料ガスを石英ガ
ラス製反応器に導入した。該反応管温度を７５０℃に制
御し、原料ガスを０．０８秒滞留するように冷却空気を
反応管に導入後、ポリテトラフルオロエチレン製バグフ
ィルターにて超微粒子状酸化チタン粉末を捕集した。[0053] Comparative Example 2: 4.7Nm 3 / hr of gaseous forty-four titanium chloride diluent gas diluted titanium tetrachloride with nitrogen gas 36 Nm 3 / hr was preheated to 800 ℃, 36Nm 3 /
An oxidizing gas in which hr air and 25 Nm 3 / hr steam were mixed was preheated to 800 ° C., and these raw material gases were introduced into a quartz glass reactor. The reaction tube temperature was controlled at 750 ° C., cooling air was introduced into the reaction tube so that the raw material gas was retained for 0.08 seconds, and then ultrafine particulate titanium oxide powder was collected by a polytetrafluoroethylene bag filter. .
【００５４】得られた酸化チタンを熱風循環加熱炉に入
れ、水と酸化チタン質量比０．０４、加熱温度３５０℃
で脱塩素した。こうして得られた酸化チタンは、ＢＥＴ
比表面積が７４ｍ2／ｇ、ルチル含有率が２％、水抽出
塩素含有率が２，８００質量ｐｐｍ、全塩素含有率が
３，９００質量ｐｐｍであった。式（１）に水抽出塩素
含有量 ２，８００質量ｐｐｍ、全塩素含有量 ３，９
００質量ｐｐｍを代入して算出される表面塩素率は８０
％よりも低く、全塩素含有率は、式（２）に比表面積７
４ｍ2／ｇを代入して算出される値よりも大きな数値を
示した。この粉末のレーザー回折式粒度分布測定法にて
測定した粒度分布における９０％累積質量粒度分布径Ｄ
９０は３．６μｍであった。ルチル化率、ＢＥＴ比表面
積、全塩素含有量、表面塩素率、Ｄ９０、及び、Ｆｅ、
Ａｌ、Ｓｉ、Ｓの分析結果を表１に示す。The obtained titanium oxide was put into a hot air circulation heating furnace, and the mass ratio of water to titanium oxide was 0.04, and the heating temperature was 350 ° C.
Dechlorinated in. The titanium oxide thus obtained is BET
The specific surface area was 74 m 2 / g, the rutile content was 2%, the water extracted chlorine content was 2,800 mass ppm, and the total chlorine content was 3,900 mass ppm. In the formula (1), the water extracted chlorine content is 2,800 mass ppm, the total chlorine content is 3,9
The surface chlorine rate calculated by substituting 00 mass ppm is 80
%, The total chlorine content is expressed by the formula (2) with a specific surface area of 7
The value was larger than the value calculated by substituting 4 m 2 / g. 90% cumulative mass particle size distribution diameter D in the particle size distribution of this powder measured by the laser diffraction type particle size distribution measurement method
90 was 3.6 μm. Rutile ratio, BET specific surface area, total chlorine content, surface chlorine ratio, D90, and Fe,
Table 1 shows the analysis results of Al, Si, and S.
【００５５】比較例３：５．９Ｎｍ3／ｈｒのガス状四
塩化チタンを３０Ｎｍ3／ｈｒの窒素ガスで希釈した四
塩化チタン希釈ガスを１，１００℃に予熱し、４Ｎｍ3
／ｈｒの酸素と１６Ｎｍ3／ｈｒの水蒸気を混合した酸
化性ガスを１，１００℃に予熱し、これらの原料ガスを
石英ガラス製反応器に導入した。該反応管温度を１，２
００℃に制御し、原料ガスを０．０４秒滞留するように
冷却空気を反応管に導入後、ポリテトラフルオロエチレ
ン製バグフィルターにて超微粒子状酸化チタン粉末を捕
集した。[0055] Comparative Example 3: 5.9Nm 3 / hr of gaseous forty-four titanium chloride diluent gas diluted titanium tetrachloride with nitrogen gas 30 Nm 3 / hr was preheated to 1,100 ° C., 4 Nm 3
/ Hr of oxygen and 16 Nm 3 / hr of water vapor were mixed to preoxidize the oxidizing gas to 1,100 ° C., and these raw material gases were introduced into the quartz glass reactor. The reaction tube temperature is 1, 2
After controlling the temperature to 00 ° C. and introducing cooling air into the reaction tube so that the raw material gas was retained for 0.04 seconds, ultrafine particulate titanium oxide powder was collected by a polytetrafluoroethylene bag filter.
【００５６】得られた酸化チタンを熱風循環加熱炉に入
れ、水と酸化チタン質量比０．０６、加熱温度４５０℃
で脱塩素した。こうして得られた酸化チタンは、ＢＥＴ
比表面積が４４ｍ2／ｇ、ルチル含有率が１２％、水抽
出塩素含有量が１，２００質量ｐｐｍ、全塩素含有量が
１，３００質量ｐｐｍであった。式（１）に水抽出塩素
含有量 １，２００質量ｐｐｍ、全塩素含有量 １，３
００質量ｐｐｍを代入して算出される表面塩素率は８０
％よりも高く、全塩素含有率は、式（２）に比表面積４
４ｍ2／ｇを代入して算出される値よりも小さな数値を
示した。この粉末のレーザー回折式粒度分布測定法にて
測定した粒度分布における９０％累積質量粒度分布径Ｄ
９０は１．２μｍであった。ルチル化率、ＢＥＴ比表面
積、全塩素含有量、表面塩素率、Ｄ９０、及び、Ｆｅ、
Ａｌ、Ｓｉ、Ｓの分析結果を表１に示す。
比較例４：市販の硫酸チタニル溶液（関東化学（株）
製、試薬１級）を煮沸し、得られた沈殿を純水で洗浄
し、含水酸化チタンを得た。この含水酸化チタンの残存
硫酸を除去するため、純水を加えスラリーとし、これを
攪拌しながらアンモニア水溶液を加えてｐＨ５に調整
し、１２時間攪拌した。この後、限外ろ過膜で含水酸化
チタン濃度を２０質量％まで濃縮した。濃縮液に再びア
ンモニア水溶液を加えてｐＨ５に調整し、１２時間攪拌
の後、純水を加えながら限外ろ過膜でろ過しチタニアゾ
ルを得た。得られたチタニアゾルを３００℃で２時間乾
燥し、液相法による超微粒子酸化チタンを得た。得られ
た酸化チタンはＢＥＴ比表面積が２１２ｍ２／ｇ、ルチ
ル含有率１％であった。水抽出塩素含有量、全塩素含有
量はともに０質量ｐｐｍであった。この酸化チタンを乳
鉢で解砕し、レーザー回折式粒度分布測定法にて粒度分
布を測定したところ、９０％累積質量粒度Ｄ９０は２
６．１μｍであった。ルチル化率、ＢＥＴ比表面積、全
塩素含有量、表面塩素率、Ｄ９０、及び、Ｆｅ、Ａｌ，
Ｓｉ，Ｓの分析結果を表１に示す。The obtained titanium oxide was put into a hot air circulation heating furnace, and the mass ratio of water to titanium oxide was 0.06, and the heating temperature was 450 ° C.
Dechlorinated in. The titanium oxide thus obtained is BET
The specific surface area was 44 m 2 / g, the rutile content was 12%, the water-extracted chlorine content was 1,200 mass ppm, and the total chlorine content was 1,300 mass ppm. Water extraction chlorine content 1,200 mass ppm, total chlorine content 1,3 in formula (1)
The surface chlorine rate calculated by substituting 00 mass ppm is 80
%, The total chlorine content is expressed by the formula (2) with a specific surface area of 4
The value is smaller than the value calculated by substituting 4 m 2 / g. 90% cumulative mass particle size distribution diameter D in the particle size distribution of this powder measured by the laser diffraction type particle size distribution measurement method
90 was 1.2 μm. Rutile ratio, BET specific surface area, total chlorine content, surface chlorine ratio, D90, and Fe,
Table 1 shows the analysis results of Al, Si, and S. Comparative Example 4: Commercially available titanyl sulfate solution (Kanto Chemical Co., Inc.)
Manufactured by Reagent Grade 1) was boiled, and the obtained precipitate was washed with pure water to obtain hydrous titanium oxide. In order to remove the residual sulfuric acid of the hydrous titanium oxide, pure water was added to form a slurry, and while stirring this, an aqueous ammonia solution was added to adjust the pH to 5, and the mixture was stirred for 12 hours. Then, the concentration of hydrous titanium oxide was concentrated to 20% by mass with an ultrafiltration membrane. Aqueous ammonia solution was added again to the concentrated liquid to adjust the pH to 5, and the mixture was stirred for 12 hours and then filtered with an ultrafiltration membrane while adding pure water to obtain a titania sol. The obtained titania sol was dried at 300 ° C. for 2 hours to obtain ultrafine particle titanium oxide by the liquid phase method. The titanium oxide obtained had a BET specific surface area of 212 m 2 / g and a rutile content of 1%. Both the water-extracted chlorine content and the total chlorine content were 0 mass ppm. When this titanium oxide was crushed in a mortar and the particle size distribution was measured by a laser diffraction type particle size distribution measuring method, the 90% cumulative mass particle size D90 was 2
It was 6.1 μm. Rutile ratio, BET specific surface area, total chlorine content, surface chlorine ratio, D90, Fe, Al,
Table 1 shows the analysis results of Si and S.
【００５７】[0057]
【表１】 [Table 1]
【００５８】[0058]
【発明の効果】本発明により、同等のＢＥＴ比表面積を
有する従来の酸化チタンに比べ、粒子内部のハロゲン含
有量が低く、分散性に特に優れた、気相法によるアナタ
ーゼ型の超微粒子酸化チタン、これを脱ハロゲンするこ
とによりＢＥＴ比表面積（Ｂ）とハロゲン含有率（Ｃ）
との関係が前記式（２）の条件を満足する酸化チタン、
レーザー回折式粒度分布測定法で測定されたＤ９０が
２．５μｍ以下の酸化チタン、及びこれらの製造方法が
提供される。EFFECTS OF THE INVENTION According to the present invention, anatase-type ultrafine titanium oxide particles by a vapor phase method, which have a lower halogen content inside the particles and are particularly excellent in dispersibility as compared with conventional titanium oxide particles having an equivalent BET specific surface area. , By dehalogenating it, BET specific surface area (B) and halogen content (C)
Titanium oxide whose relationship with the above satisfies the condition of the above formula (2),
Provided are titanium oxides having a D90 measured by a laser diffraction type particle size distribution measurement method of 2.5 μm or less, and methods for producing these.
【００５９】本発明の酸化チタンは、光触媒用途や太陽
電池用途等に好適であり、特に、水系の溶媒に対する分
散性が優れるので、水中での光触媒用途に好適に用いる
ことができ、粉体としても解砕工程等が不要もしくは極
めて軽微な設備で済み、工業的に非常に大きな実用的価
値を有するものである。The titanium oxide of the present invention is suitable for photocatalyst applications, solar cell applications and the like. In particular, since it has excellent dispersibility in an aqueous solvent, it can be suitably used for photocatalyst applications in water, and as a powder. Also, it does not require a disintegration step or requires extremely small equipment, and has a very large industrial value in industry.
【図１】超微粒子状酸化チタンのハロゲン含有率とＢＥ
Ｔ比表面積との関係を示す。1] Halogen content and BE of ultrafine particulate titanium oxide
The relationship with the T specific surface area is shown.
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Claims (36)
スとを反応させることにより得られる酸化チタンであっ
て、ルチル含有率が５％以下で、かつ、ＢＥＴ一点法で
測定した酸化チタンの比表面積をＢ（ｍ2／ｇ）、酸化
チタンの全ハロゲン含有量をＣ（質量ｐｐｍ）としたと
き、 Ｃ≦６５０ｅ0.02B で示され、且つ、１質量％の水懸濁液とした時に、その
水懸濁液を２０℃で３０分間放置後、酸化チタンに含ま
れていたハロゲン量の８０質量％以上のハロゲンが液相
に移行することを特徴とする酸化チタン。1. A titanium oxide obtained by reacting a gas containing titanium halide with an oxidizing gas, which has a rutile content of 5% or less and a ratio of titanium oxide measured by a BET single point method. When the surface area is B (m 2 / g) and the total halogen content of titanium oxide is C (mass ppm), C ≦ 650e 0.02B , and when a 1 mass% water suspension is used, Titanium oxide characterized in that after the aqueous suspension is left at 20 ° C. for 30 minutes, 80% by mass or more of the halogen contained in titanium oxide moves to the liquid phase.
９０質量％以上のハロゲンが液相に移行する請求項１に
記載の酸化チタン。2. The titanium oxide according to claim 1, wherein 90% by mass or more of halogen contained in titanium oxide is transferred to a liquid phase.
の各元素をそれぞれ１００質量ｐｐｍ以下含む請求項１
または２に記載の酸化チタン。3. Titanium oxide is Fe, Al, Si and S
2. Each element of the above is contained in an amount of 100 mass ppm or less.
Alternatively, the titanium oxide described in 2.
比表面積を持つ請求項１乃至３に記載の酸化チタン。4. The titanium oxide according to claim 1, wherein the titanium oxide has a specific surface area of 10 to 200 m 2 / g.
請求項１乃至４に記載の酸化チタン。5. The titanium oxide according to claim 1, wherein the main phase of titanium oxide is anatase.
％以上である請求項５に記載の酸化チタン。6. The anatase content of titanium oxide is 90.
% Or more, the titanium oxide according to claim 5.
る請求項１乃至４に記載の酸化チタン。7. The titanium oxide according to claim 1, wherein the main phase of titanium oxide is brookite.
％以上である請求項７の酸化チタン。8. The brookite content of titanium oxide is 90.
% Of titanium oxide.
計によって測定される２．５μｍ以下の９０％累積質量
粒度分布径を持つ、請求項１乃至８のいずれか１項に記
載の酸化チタン。9. The titanium oxide according to claim 1, wherein the titanium oxide has a 90% cumulative mass particle size distribution diameter of 2.5 μm or less measured by a laser diffraction particle size analyzer.
であり、前記ハロゲンが塩素である請求項１乃至９のい
ずれか１項に記載の酸化チタン。10. The titanium oxide according to claim 1, wherein the titanium halide is titanium tetrachloride and the halogen is chlorine.
ガスとを反応させることにより酸化チタンを製造する気
相法において、ハロゲン化チタンを含むガス及び酸化性
ガスをそれぞれ反応器に導入し反応させたとき、該反応
器内の温度が８００℃以上１，１００℃未満であること
を特徴とする酸化チタンの製造方法。11. In a gas phase method for producing titanium oxide by reacting a gas containing titanium halide with an oxidizing gas, a gas containing titanium halide and an oxidizing gas are introduced into a reactor and reacted. At that time, the temperature in the reactor is 800 ° C. or higher and lower than 1,100 ° C., the method for producing titanium oxide.
性ガスが、反応器内で８００℃以上１，１００℃未満の
温度の滞留時間が０．１秒以下である請求項１１に記載
の酸化チタンの製造方法。12. The titanium oxide according to claim 11, wherein the gas containing titanium halide and the oxidizing gas have a residence time of 0.1 second or less at a temperature of 800 ° C. or higher and lower than 1,100 ° C. in the reactor. Manufacturing method.
性ガスが、それぞれ、６００℃以上、１，１００℃未満
に予熱されて反応器に導入される請求項１１または１２
に記載の酸化チタンの製造方法。13. The gas containing titanium halide and the oxidizing gas are introduced into the reactor after being preheated to 600 ° C. or higher and lower than 1,100 ° C., respectively.
The method for producing titanium oxide according to.
し不活性ガス０．１〜２０モルの割合で混合した原料ガ
スと、ハロゲン化チタン１モルに対し１〜３０モルの酸
化性ガスとで行われる請求項１１乃至１３のいずれか１
項に記載の酸化チタンの製造方法。14. The reaction is carried out by mixing a raw material gas mixed with 1 mol of titanium halide in an amount of 0.1 to 20 mol of an inert gas and 1 to 30 mol of oxidizing gas with respect to 1 mol of titanium halide. Any one of claims 11 to 13 to be performed.
The method for producing titanium oxide according to the item.
であることを特徴とする請求項１１乃至１４のいずれか
１項に記載の酸化チタンの製造方法。15. The method for producing titanium oxide according to claim 11, wherein the oxidizing gas is oxygen gas containing water vapor.
し、水蒸気０．１モル以上を含む請求項１５に記載の酸
化チタンの製造方法。16. The method for producing titanium oxide according to claim 15, wherein the oxidizing gas contains 0.1 mol or more of water vapor with respect to 1 mol of oxygen gas.
である請求項１１乃至１６のいずれか１項に記載の酸化
チタンの製造方法。17. The method for producing titanium oxide according to claim 11, wherein the titanium halide is titanium tetrachloride.
記載の製造方法で製造された酸化チタンを乾式でハロゲ
ンを除去することを特徴とする酸化チタンの製造方法。18. A method for producing titanium oxide, wherein the titanium oxide produced by the production method according to claim 11 is removed in a dry manner to remove halogen.
化チタンを２００〜５００℃に加熱することにより行う
方法である請求項１８に記載の酸化チタンの製造方法。19. The method for producing titanium oxide according to claim 18, wherein the method of removing halogen by dry method is a method of heating titanium oxide to 200 to 500 ° C.
蒸気を含有するガスを２００〜１０００℃に加熱し、酸
化チタンと接触させながら行なう方法である請求項１８
に記載の酸化チタンの製造方法。20. The dry method of removing halogen is a method of heating a gas containing water vapor to 200 to 1000 ° C. and bringing it into contact with titanium oxide.
The method for producing titanium oxide according to.
０．１容量％以上含む空気である請求項２０に記載の酸
化チタンの製造方法。21. The method for producing titanium oxide according to claim 20, wherein the gas containing water vapor is air containing 0.1% by volume or more of water vapor.
０．０１以上である請求項２０に記載の酸化チタンの製
造方法。22. The method for producing titanium oxide according to claim 20, wherein the water vapor is 0.01 or more in mass ratio with respect to titanium oxide.
記載の製造方法で製造された酸化チタンを湿式でハロゲ
ンを除去し、酸化チタンを含むスラリーを得ることを特
徴とする酸化チタンの製造方法。23. Titanium oxide produced by the production method according to claim 11, wherein halogen is removed by a wet process to obtain a slurry containing titanium oxide. Method.
化チタンを水に懸濁させ、液相に移行したハロゲンを系
外に分離する方法である請求項２３に記載の酸化チタン
の製造方法。24. The method for producing titanium oxide according to claim 23, wherein the method of removing halogen by a wet method is a method of suspending titanium oxide in water and separating the halogen transferred to a liquid phase out of the system.
ロゲンの分離を限外ろ過膜で行う方法である請求項２３
または２４に記載の酸化チタンの製造方法。25. The method of removing halogen by a wet method is a method of separating halogen by an ultrafiltration membrane.
Or the method for producing titanium oxide according to 24.
ロゲンの分離を逆浸透膜で行う方法である請求項２３ま
たは２４に記載の酸化チタンの製造方法。26. The method for producing titanium oxide according to claim 23, wherein the method of removing halogen by a wet method is a method of separating halogen by a reverse osmosis membrane.
ロゲンの分離をフィルタープレスで行う方法である請求
項２３または２４に記載の酸化チタンの製造方法。27. The method for producing titanium oxide according to claim 23 or 24, wherein the method of removing the halogen by a wet method is a method of separating the halogen by a filter press.
記載の製造方法で製造された酸化チタンを含むことを特
徴とする粉体。28. A powder comprising titanium oxide produced by the production method according to any one of claims 11 to 27.
記載の製造方法で製造された酸化チタンを含むことを特
徴とするスラリー。29. A slurry comprising the titanium oxide produced by the production method according to claim 11.
記載の製造方法で製造された酸化チタンを含むことを特
徴とする組成物。30. A composition comprising the titanium oxide produced by the production method according to any one of claims 11 to 27.
記載の製造方法で製造された酸化チタンを含むことを特
徴とする光触媒材料。31. A photocatalyst material comprising titanium oxide produced by the production method according to claim 11.
記載の製造方法で製造された酸化チタンを含むことを特
徴とする湿式太陽電池用材料。32. A wet solar cell material, comprising titanium oxide produced by the production method according to any one of claims 11 to 27.
記載の製造方法で製造された酸化チタンを含むことを特
徴とする誘電体原料。33. A dielectric material, comprising the titanium oxide produced by the production method according to any one of claims 11 to 27.
記載の製造方法で製造された酸化チタンを含むことを特
徴とするシリコーンゴム添加剤。34. A silicone rubber additive, characterized by comprising titanium oxide produced by the production method according to any one of claims 11 to 27.
法で測定した比表面積が１０〜２００ｍ2／ｇ、レーザ
ー回折式粒度分析計によって測定される９０％累積質量
粒度分布径が２．５μｍ以下の酸化チタン粒子であり、
かつ、ＢＥＴ一点法で測定した酸化チタンの比表面積を
Ｂ（ｍ2／ｇ）、酸化チタン粒子内部のハロゲン含有量
をＣi（質量ｐｐｍ）としたとき、粒子内部に含まれる
ハロゲン量が０≦Ｃi≦６５０ｋｅ0.02B（ｋは０．２
０）で示されることを特徴とする酸化チタン粒子。35. The rutile content is 5% or less, the specific surface area measured by the BET single point method is 10 to 200 m 2 / g, and the 90% cumulative mass particle size distribution diameter measured by a laser diffraction particle size analyzer is 2.5 μm. The following titanium oxide particles,
When the specific surface area of titanium oxide measured by the BET one-point method is B (m 2 / g) and the halogen content in the titanium oxide particles is C i (mass ppm), the amount of halogen contained in the particles is 0. ≤C i ≤650 ke 0.02B (k is 0.2
0) Titanium oxide particles characterized by being represented by 0).
０．１５）で示される量のハロゲンを粒子内部に含む請
求項３５に記載の酸化チタン粒子。36. The titanium oxide particles according to claim 35, wherein an amount of halogen represented by 10 <C i ≦ 650 ke 0.02 B (k is 0.15) is contained inside the particles.
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