JPH0214819A - Production of alumina-coated titanium oxide powder - Google Patents
Production of alumina-coated titanium oxide powderInfo
- Publication number
- JPH0214819A JPH0214819A JP63164594A JP16459488A JPH0214819A JP H0214819 A JPH0214819 A JP H0214819A JP 63164594 A JP63164594 A JP 63164594A JP 16459488 A JP16459488 A JP 16459488A JP H0214819 A JPH0214819 A JP H0214819A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- sol
- alumina
- oxide powder
- component
- 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.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 60
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000000843 powder Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000460 chlorine Substances 0.000 claims abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 239000011593 sulfur Substances 0.000 claims abstract description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 4
- 230000008719 thickening Effects 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000010292 electrical insulation Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- -1 methyl ethyl Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- DAOVYDBYKGXFOB-UHFFFAOYSA-N tris(2-methylpropoxy)alumane Chemical compound [Al+3].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] DAOVYDBYKGXFOB-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Abstract
Description
酸化チタン粉末は基本的な白色前車４であり、従来から
白色インキ、白色塗料の顔料ヘヒクル成分として用いら
れてきたが、最近ではプラス千ンクス用フィラー、アル
ミニウム蒸着箔用特殊インキ、セラミンクス材料あるい
は誘電体材料等としての用途が増加してきている。Titanium oxide powder is a basic white material4, and has traditionally been used as a pigment vehicle component in white ink and white paint, but recently it has been used as a filler for Plus Thousand Inx, special ink for aluminum vapor-deposited foil, ceramic material, etc. Its use as a dielectric material, etc. is increasing.
酸化チタン粉末の光安定性と化学安定性を増大させるた
めに、その表面をアルミナ、シリカ、ジルコニアまたは
プラスチックスで被覆することがすでに行われており、
特にアルミナ被覆は重要視されている。
この方法としてはアルミニウム塩またはアルミン酸塩の
水溶液を酸化チタン粉末に接触させ、次いで該溶液のｐ
Ｈを変化させる方法によって水酸化アルミニウム皮膜を
酸化チタンの表面に形成させるとか、水酸化アルミニウ
ムを酸化チタン粉末に単に混合するだけで被覆させると
かの操作を行なった後、焼成して得られた製品が市販さ
れている。ところがこのような製品は一般に塩素分、イ
オウ分またはアルカリ金属分がかなり含まれておりかつ
酸化チタン粉末表面の被覆液態が均一、完全とは言えず
常に品質のすぐれたものを製造することが困難であった
。To increase the photostability and chemical stability of titanium oxide powder, coating its surface with alumina, silica, zirconia or plastics has already been done;
Particular emphasis is placed on alumina coating. This method involves bringing an aqueous solution of an aluminum salt or aluminate into contact with titanium oxide powder, and then
A product obtained by firing after performing operations such as forming an aluminum hydroxide film on the surface of titanium oxide by changing H, or coating it by simply mixing aluminum hydroxide with titanium oxide powder. is commercially available. However, such products generally contain considerable amounts of chlorine, sulfur, or alkali metals, and the coating liquid on the surface of the titanium oxide powder is not uniform or perfect, making it difficult to consistently produce products of excellent quality. Met.
従来のアルミナ、シリカ、ジルコニアまたはプラスチッ
クスで被覆された酸化チタン粉末は、いずれも被覆が美
しく均一に行なわれていないため光安定性とか電気絶縁
性が悪いとか場合によってはアルミニウム蒸着面を腐蝕
する等の欠点があるほか酸化チタン製品の表面酸度が一
定でなかったり顔料としての分散性とか光安定性が悪い
とかψ問題点があった。Conventional titanium oxide powders coated with alumina, silica, zirconia, or plastics are not coated beautifully and uniformly, resulting in poor photostability and electrical insulation, and in some cases corroding the aluminum-deposited surface. In addition to these drawbacks, titanium oxide products also have problems such as uneven surface acidity, poor pigment dispersibility, and poor light stability.
本発明者らは、以上のような問題点を解決するために、
アルミナ被覆酸化チタン粉末の製造方法について研究を
重ねた結果、塩素分およびイオウ分の合計が０．０５重
量％以下である酸化チタン粉末とアルミニウムアルコラ
ートから作られた高純度水酸化アルミニウムを含むゾル
との混合物を溶剤中に分散した杖態において６０〜３０
０’Ｃに保ち酸化チタン粒子表面のゾル成分をゲル成分
に変化せしめた後余分のゾル成分、溶剤もしくはこれら
の両者を除去して得られた粉末を３００〜ｌ０００℃で
焼成することにより前記問題点を解決し得ることを見い
だしたのである。ここにおいて酸化チタンとしては、ル
チル型酸化チタン、アナターゼ型酸化チタンもしくはこ
れらの混合物のいずれかで、塩素分およびイオウ分の合
計が０．０５重量％以下のものを用いることが必要であ
る。そしてこの塩素分およびイオウ分の合計が０．０５
重量％より多いと、この発明の方法で酸化チタンにアル
ミナを被覆した製品としても、長期の使用期間中に、塩
素分やイオウ分が浸出してきてアルミナ層に吸着され安
定性とか電気絶縁性が悪くなったり、またアルミニウム
蒸着面を腐蝕したりする等の嫌悪すべき問題を惹起する
。
また、水酸化アルミニウムを含むゾルとしては、炭素原
子数が１〜４個であるアルキル基を含むトリアルコキシ
アルミニウムであるアルミニウムアルコラートから作ら
れた高純度水酸化アルミニウムを含むゾルを用いること
が肝要である。そして高純度とは、実質的に塩素分、イ
オウ分またはアルカリ金属分を含んでいないことである
。またゾルに含有されるアルミナの割合としては１〜３
０重量％がよい、この割合が１重量％より少ない場合に
は水酸化アルミニウムゾルが酸化チタンに均一被覆せし
めることが難しくなり、また３０重量％より多い場合に
はゾルの粘度が高くなりすぎて脱気とか被覆膜のレベリ
ング作業が容易でなくなる。
本発明の溶剤としては水、水溶性有機溶剤および疎水性
有機溶剤を含む水溶性有機溶剤よりなる群から選ばれた
少なくとも一つの液体である。この溶剤は酸化チタン粒
子表面に付着したゾルをゲルにする反応を完成するため
に都合がよいものであり沸点が常圧下での６０〜３００
°Ｃであるものが都合がよい。この溶剤は各種あるが、
水酸化アルミニウムゾルの分散性を考慮すると水、また
は水と親和性の強い溶剤がよく、たとえばアルコール系
ではエタノール、イソプロパツール、２−ブタノール、
ｔ−フタノール、エチレングリコール、プロピレングリ
コール、ジエチレングリコール、２−エチル−２−（ヒ
ドロキシメチル）−１，３−プロパンジオール等があり
、エーテル系ではテトロヒト「Ｉフラン、１，２−ジェ
トキシエタン、ジオキソラン、ジオキサン、ジエチレン
グリコールジエチルエーテル等があり、ケトン系ではメ
チルエチルゲトン、ジエチルケトン、アセチルアセトン
、シクロペンタノン、シクロヘキサノン等があり、窒素
化合物系ではアセトニトリル、ジメチルホルムアミド、
ジメチルアセタミド、ピロール、イミダゾール、オキサ
ゾリドン、アニリン、ピリジン、Ｎ−メチルピロリドン
等がある。
本発明のアルミニウムアルコラートとしては、アルミニ
ウムメチレート、アルミニウムメチレート、アルミニウ
ムイソプロピレート、トリ（イソブトキシ）アルミニウ
ム、１−リ（ｎ−ブトキシ）アルミニウム、ノ（イソブ
トキシンモノ−２−）゛トキシアルミニウム等がある。
さて次に本発明の操作方法ならびに条件について説明し
よう。
酸化チタンと水酸化アルミニウムを含むゾルとを混合す
る際の例として？１ｉ合比は酸化チタン分（ＴｉＯｚ）
に対し、ゾル中のアルミナ分（ＡＩｚＯｔ）の割合を１
０重量％前後にすると実施が容易である。精製された酸
化チタンを水酸化アルミニウムを含むゾル中に投入して
混合した後、２０°Ｃで１時間以」二撹拌してゾルを酸
化チタン粒子表面に均一に展着させた後、さらに９５°
Ｃで１時間撹拌し、水酸化アルミニウムゾルの付着を緊
密にならしめる。この際、ゾルの大部分はゲル化して酸
化チタン表面に沈着することが認められる。このような
混合物を常圧下で処理する一方法としては、これを遠心
分離法あるいはろ適法により沈澱物を分取して水洗して
余分なゾルを除去した後、溶剤中に再分散させることが
１１１奨される。もちろん、上記の他の方法によって酸
化チタン粉末と水酸化アルミニウムゾルとが効果的に混
合されてもよいがこの混合物は溶剤中に分散した状態で
なければならない。この酸化チタンを分散させた混合物
を次に６０〜３００°Ｃ特に好ましくは８０〜１８０°
Ｃに保ち（溶剤の場合には煮沸することが便利であり、
水の場合には加圧下で熱水塾成させる。）たとえば数時
間加熱損Ｆ］゛シ、酸化チタンに付着している水酸化ア
ルミニウムのゾル成分をゲル成分に変換するまで続けら
れる。
次いでこれをたとえばフラッシュエバポレーターなどで
脱溶剤することにより水酸化アルミニウム（たとえばア
ルミナ水和物−水和物）が被覆している酸化チタンの粉
末が収率よく得られる。これを−旦乾燥後３００〜１０
００’Ｃ特に好ましくは３５０〜７００°Ｃで焼成する
ことにより、アルミナが表面に均一に被覆した酸化チタ
ンの粉体が得られるのである。このようにして得られた
製品はｍｍに光安定性、電気絶縁性がよくかつ各粒子の
表面酸度が一定であり、顔料としての分散性のよいアル
ミナ被覆酸化チタン粉末としての性質が付与される。こ
の水酸化アルミニウムを含むゾルの被覆の際に必要性が
あれば、シリカゾル、ジルコニアゾルまたは増粘防止剤
のいずれかあるいはこれらの２種以上の混合物を含んで
いてもよいのは当然であり、特に増粘防止剤（ポリオー
ル類、酸アミド類）の使用は水酸化アルミニウムを含む
ゾルの均一被覆を保証する上で大切である。In order to solve the above problems, the present inventors
As a result of repeated research on the manufacturing method of alumina-coated titanium oxide powder, we found that a sol containing high-purity aluminum hydroxide made from titanium oxide powder and aluminum alcoholate with a total chlorine and sulfur content of 0.05% by weight or less. 60 to 30 in the form of a stick dispersed in a solvent.
The above problem can be solved by keeping the temperature at 0'C and converting the sol component on the surface of the titanium oxide particles into a gel component, and then removing the excess sol component, solvent, or both, and firing the resulting powder at 300 to 1,000 degrees Celsius. They discovered that the problem could be solved. As the titanium oxide, it is necessary to use rutile-type titanium oxide, anatase-type titanium oxide, or a mixture thereof, with a total chlorine content and sulfur content of 0.05% by weight or less. And the total of this chlorine content and sulfur content is 0.05
If it exceeds the weight percentage, even if titanium oxide is coated with alumina using the method of this invention, chlorine and sulfur will leach out and be adsorbed to the alumina layer during long-term use, resulting in a loss of stability and electrical insulation. This causes unpleasant problems such as deterioration and corrosion of the aluminum evaporated surface. Furthermore, as the sol containing aluminum hydroxide, it is important to use a sol containing high-purity aluminum hydroxide made from aluminum alcoholate, which is trialkoxyaluminum containing an alkyl group having 1 to 4 carbon atoms. be. High purity means that it does not substantially contain chlorine, sulfur, or alkali metals. Also, the proportion of alumina contained in the sol is 1 to 3.
0% by weight is better; if this percentage is less than 1% by weight, it will be difficult to uniformly coat titanium oxide with aluminum hydroxide sol, and if it is more than 30% by weight, the viscosity of the sol will become too high. It becomes difficult to perform deaeration and leveling of the coating film. The solvent of the present invention is at least one liquid selected from the group consisting of water, water-soluble organic solvents, and water-soluble organic solvents including hydrophobic organic solvents. This solvent is convenient for completing the reaction of turning the sol attached to the surface of the titanium oxide particles into a gel, and has a boiling point of 60 to 300 at normal pressure.
°C is convenient. There are various types of this solvent, but
Considering the dispersibility of aluminum hydroxide sol, it is best to use water or a solvent with strong affinity for water.For example, alcohol-based solvents include ethanol, isopropanol, 2-butanol,
These include t-phthanol, ethylene glycol, propylene glycol, diethylene glycol, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, etc. Among the ethers, there are t-phthanol, ethylene glycol, propylene glycol, diethylene glycol, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, etc.; , diethylene glycol diethyl ether, etc. Ketones include methyl ethyl getone, diethyl ketone, acetylacetone, cyclopentanone, cyclohexanone, etc. Nitrogen compounds include acetonitrile, dimethylformamide,
Examples include dimethylacetamide, pyrrole, imidazole, oxazolidone, aniline, pyridine, and N-methylpyrrolidone. Examples of the aluminum alcoholate of the present invention include aluminum methylate, aluminum methylate, aluminum isopropylate, tri(isobutoxy)aluminum, 1-ly(n-butoxy)aluminum, non-(isobutoxine mono-2-)゛toxyaluminum, etc. There is. Next, the operating method and conditions of the present invention will be explained. What is an example of mixing titanium oxide and a sol containing aluminum hydroxide? 1i combined ratio is titanium oxide (TiOz)
In contrast, the ratio of alumina content (AIzOt) in the sol is 1
It is easy to implement when the amount is around 0% by weight. After adding purified titanium oxide to a sol containing aluminum hydroxide and mixing, the mixture was stirred at 20°C for more than 1 hour to spread the sol uniformly on the surface of the titanium oxide particles, and then further mixed with 95°C. °
Stir for 1 hour at C to even out the adhesion of the aluminum hydroxide sol. At this time, it is observed that most of the sol is gelled and deposited on the titanium oxide surface. One way to treat such a mixture under normal pressure is to separate the precipitate by centrifugation or filtration, wash it with water to remove excess sol, and then redisperse it in a solvent. 111 recommended. Of course, the titanium oxide powder and aluminum hydroxide sol may be effectively mixed by other methods described above, but this mixture must be in a dispersed state in the solvent. The mixture in which this titanium oxide is dispersed is then heated at a temperature of 60 to 300°C, particularly preferably 80 to 180°C.
C (in the case of solvents, it is convenient to boil them,
In the case of water, it is heated under pressure. ) For example, heating is continued for several hours until the sol component of aluminum hydroxide adhering to titanium oxide is converted into a gel component. Next, by removing the solvent from this using a flash evaporator or the like, titanium oxide powder coated with aluminum hydroxide (eg, alumina hydrate-hydrate) can be obtained in good yield. After drying this, 300 ~ 10
By firing at 00'C, particularly preferably at 350 to 700C, titanium oxide powder whose surface is uniformly coated with alumina can be obtained. The product thus obtained has good photostability and electrical insulation properties, and the surface acidity of each particle is constant, giving it the properties of an alumina-coated titanium oxide powder with good dispersibility as a pigment. . Of course, when coating the sol containing aluminum hydroxide, it may contain silica sol, zirconia sol, or a thickening inhibitor, or a mixture of two or more of these, if necessary. In particular, the use of thickening inhibitors (polyols, acid amides) is important in ensuring uniform coverage of the sol containing aluminum hydroxide.
本発明の方法では、酸化チタン粉末に対してアルミナの
被覆が完全に行なわれており、そのアルミナは高純度ア
ルミナであり場合によってはかなり活性であるので酸化
チタンからもし不純物として微計の塩素分とかイオウ分
とかが溶出してきたとしてもアルミナ層にトランプされ
実際的に酸化チタン粉末からは塩素分、イオウ分は検出
されることが少ないのである。
本発明の方法によるときはアルミナで被覆された酸化チ
タン粉末が二次的なｉＪ［を起こすことが少なく、乾燥
表面の二次処理が容易であり、プラスチ・ノクスや溶剤
への分散性も相当によく、公知に属する製造法で得た製
品とは格段に品質上の優越性があるのである。
本発明者らは以上の本発明の方法に関し多数の実験を行
ない本発明の優秀性を明らかにしてきたが、以下にその
中から代表的な例を抽出して本発明の技術的内容を説明
することにする。In the method of the present invention, the titanium oxide powder is completely coated with alumina, and since the alumina is high-purity alumina and is quite active in some cases, if the titanium oxide contains minute amounts of chlorine as impurities. Even if chlorine or sulfur were to be eluted, they would be trapped in the alumina layer and, in practice, chlorine and sulfur would be rarely detected in titanium oxide powder. When using the method of the present invention, the alumina-coated titanium oxide powder rarely causes secondary iJ[, the secondary treatment of the dry surface is easy, and the dispersibility in plasti-nox and solvents is also excellent. It has a much superior quality compared to products obtained using known manufacturing methods. The present inventors have conducted a large number of experiments regarding the method of the present invention and have clarified the superiority of the present invention. Below, representative examples will be extracted from among them and the technical contents of the present invention will be explained. I decided to do it.
【実施例］
実新Ｉ帽七
塩素分が０．００１重星％、イオウ分が０．０１重世％
のルチル型酸化チタン粉末（粒度３００メツシユ）３０
ｇをアルミニウムイソプロポキシドを純水中で酢酸触媒
の存在下で加水分解して作られた１重量％のアルミナ（
ＡｌｚＯｓ）を含んでいる高純度水酸化アルミニウムの
水性ゾル３００ｇに投入し、まず２５°Ｃで１時間、９
０°Ｃで２時間撹拌する。次いでこれを２５°Ｃに冷却
後、遠心分離（２９００回転／分で５分間）し、上澄を
除去する。ここで得られた沈澱物を純水で充分洗浄した
のち、ジエチレングリコール３００ｇ中に投入して２０
０°Ｃで２時間加熱撹拌する。
これを再び遠心分離し、沈澱物を分取してメタノール１
００ｇ中に分散させた後フラッシュエバポレーターで減
圧脱溶剤した後、４５０℃で３時間焼成すると、粒子表
面が均一にγ−アルミナで被覆されたルチル型酸化チタ
ン２７ｇが得られた。
月１例」工
塩素分が０．０２ｆｆｔｆｆｉ％、イオウ分は含まれて
いないアナターゼ型酸化チタン１００ｇをトリエトキシ
アルミニウムおよびテトラエチルシリケートの混合物を
エタノール中でアンモニア加水分解して作られた１０ｆ
ｆｌｆｆｉ％のアルミナ（＾１□０．）と１重量％のシ
リカ（Ｓｉｎｇ）を含んでいる水酸化アルミニウムを含
むゾル１０００ｇに投入して激しく撹拌して分散させた
後、８０°Ｃで１時間撹拌して酸化チタンの被覆を行な
う。次にこれをＩＯ’ｃに冷却後ろ過し、さらに沈澱物
を純水で充分洗浄する。次いで沈澱物を２−ブタノール
１０００ｇ中に投入して撹拌して分散しその沸点で３時
間処理した後フラッシュエバポレーターで溶剤を除去す
ると粉体が得られるので、これを５００℃で１時間焼成
すると、均一にアルミナで被覆されたアナターゼ型酸化
チタン粉末９５ｇが得られた。
実隻択主
塩素分が０．０１重量％、イオウ分が０．０４重量％の
ルチル型酸化チタン５ｋｇをアルミニウムメチレートを
純水中で酢酸触媒の存在下で加水分解して作られた３０
重量％のアルミナと、増粘防止剤としてジメチルアセト
アミドを１０重世％含む高純度水酸化アルミニウムのゾ
ル５０ｋｇに分散させた後、９０°Ｃで１時間撹拌する
。これをろ過し、さらに沈澱物を水洗する。この後沈澱
物をトリエチレングリコール５０ｋｇ中に分散し、２５
０°Ｃで１時間撹拌したのちこれを再びろ過し、沈澱物
を３５０℃で５時間焼成すると、均一にアルミナで被覆
されたルチル型酸化チタン粉末４．１３ｋｇが得られた
。
災施尉土
塩素分が０．０２重量％、イオウ分が０．０２重量％の
ルチル型とアナターゼ型がｌ：１の割合で混合されてい
る酸化チタン２ｋｇを２重量％のアルミナを含んでいる
トリ（ｎ−ブトキシ）アルミニウムを純水中で硝酸触媒
の存在下で加水分解して作られた高純度水酸化アルミニ
ウムのゾル２０ｋｇに分散させた後９５°Ｃで５時間撹
拌する。これを２５℃に冷却後、遠心分離（３５００回
転／分で５分間）し、上澄を除去する。この沈澱物を水
洗したのちジエチレングリコールジエチルエーテル２０
ｋｇに分散し煮沸しながら４時間撹拌する。冷却後注１
／ｉ物を分取して真空下で溶剤を除去した後９００℃Ｔ
：１時間焼成すると、均一にα−アルミナで被覆された
ルチル型とアナターゼ型がｔｉｔに混合している酸化チ
タン粉末１．９ｋｇが得られた。
【発明の効果】
本発明のアルミナ被覆酸化チタン粉末の製造方法によれ
ば、光安定性、電気絶縁性がよく、蒸着面を腐蝕するこ
ともなく、製品の表面酸度を一定に保ち、顔料としての
分散性のよいアルミナ被覆酸化チタン粉末を得ることが
できる。
特許出願人 日本写真印刷株式会社[Example] Jitsushin I Heptachlorine content is 0.001 double star, sulfur content is 0.01 double star
Rutile type titanium oxide powder (particle size 300 mesh) 30
1% by weight of alumina (g) prepared by hydrolyzing aluminum isopropoxide in pure water in the presence of an acetic acid catalyst.
AlzOs) was added to 300 g of an aqueous sol of high purity aluminum hydroxide containing AlzOs), and first heated at 25°C for 1 hour at 9°C.
Stir at 0°C for 2 hours. Then, after cooling it to 25°C, it is centrifuged (at 2900 rpm for 5 minutes) and the supernatant is removed. After thoroughly washing the precipitate obtained here with pure water, it was poured into 300 g of diethylene glycol for 20 min.
Heat and stir at 0°C for 2 hours. Centrifuge this again, separate the precipitate, and methanol 1
After dispersing the particles in 0.00 g, the solvent was removed under reduced pressure using a flash evaporator, and then calcined at 450° C. for 3 hours to obtain 27 g of rutile-type titanium oxide whose particle surfaces were uniformly coated with γ-alumina. 100g of anatase-type titanium oxide with a chlorine content of 0.02fftffi% and no sulfur content, made by hydrolyzing a mixture of triethoxyaluminum and tetraethylsilicate with ammonia in ethanol.
The mixture was poured into 1000 g of a sol containing aluminum hydroxide containing flfffi% alumina (^1□0.) and 1 wt% silica (Sing), stirred vigorously to disperse, and then heated at 80°C for 1 hour. Stir to coat with titanium oxide. Next, this is cooled to IO'c and filtered, and the precipitate is thoroughly washed with pure water. Next, the precipitate was poured into 1000 g of 2-butanol, stirred and dispersed, and treated at its boiling point for 3 hours. The solvent was then removed using a flash evaporator to obtain a powder, which was then calcined at 500°C for 1 hour. 95 g of anatase-type titanium oxide powder uniformly coated with alumina was obtained. 30 made by hydrolyzing 5 kg of rutile-type titanium oxide with a main chlorine content of 0.01% by weight and a sulfur content of 0.04% by weight with aluminum methylate in pure water in the presence of an acetic acid catalyst.
After dispersing in 50 kg of a sol of high purity aluminum hydroxide containing 10% by weight of alumina and 10% by mass of dimethylacetamide as a thickening inhibitor, the solution was stirred at 90°C for 1 hour. This is filtered and the precipitate is further washed with water. After this, the precipitate was dispersed in 50 kg of triethylene glycol,
After stirring at 0°C for 1 hour, this was filtered again, and the precipitate was calcined at 350°C for 5 hours to obtain 4.13 kg of rutile-type titanium oxide powder uniformly coated with alumina. 2 kg of titanium oxide, which is a mixture of rutile type and anatase type with a chlorine content of 0.02% by weight and a sulfur content of 0.02% by weight in a ratio of 1:1, and alumina of 2% by weight. A sol of 20 kg of high-purity aluminum hydroxide prepared by hydrolyzing tri(n-butoxy)aluminum in pure water in the presence of a nitric acid catalyst is dispersed and stirred at 95° C. for 5 hours. After cooling this to 25°C, it is centrifuged (3500 rpm for 5 minutes) and the supernatant is removed. After washing this precipitate with water, diethylene glycol diethyl ether 20
kg and stirred for 4 hours while boiling. After cooling Note 1
After separating the /i product and removing the solvent under vacuum, the temperature was 900°C.
: After firing for 1 hour, 1.9 kg of titanium oxide powder containing a mixture of rutile type and anatase type uniformly coated with α-alumina was obtained. Effects of the Invention According to the method for producing alumina-coated titanium oxide powder of the present invention, it has good photostability and electrical insulation, does not corrode the vapor deposition surface, keeps the surface acidity of the product constant, and can be used as a pigment. Alumina-coated titanium oxide powder with good dispersibility can be obtained. Patent applicant Nissha Printing Co., Ltd.
Claims (1)
である酸化チタン粉末とアルミニウムアルコラートから
作られた高純度水酸化アルミニウムを含むゾルとの混合
物を溶剤中に分散した状態において６０〜３００℃に保
ち酸化チタン粒子表面のゾル成分をゲル成分に変化せし
めた後余分のゾル成分、溶剤もしくはこれらの両者を除
去して得られた粉末を３００〜１０００℃で焼成するこ
とを特徴とするアルミナ被覆酸化チタン粉末の製造方法
。 ２、酸化チタンがルチル型酸化チタン、アナターゼ型酸
化チタンもしくはこれらの混合物のいずれかである請求
項１記載のアルミナ被覆酸化チタン粉末の製造方法。 ３、アルミニウムアルコラートが炭素原子数が１〜４個
であるアルキル基を含むトリアルコキシアルミニウムで
ある請求項１記載のアルミナ被覆酸化チタン粉末の製造
方法。 ４、高純度水酸化アルミニウムを含むゾルが１〜３０重
量％のアルミナ分を含んでおり実質的に塩素分、イオウ
分またはアルカリ金属分を含んでいない請求項１記載の
アルミナ被覆酸化チタン粉末の製造方法。 ５、高純度水酸化アルミニウムを含むゾルが要すれば二
次的成分としてシリカゾル、ジルコニアゾルまたは増粘
防止剤のいずれかあるいはこれらの２種以上の混合物を
含んでいる請求項１または４記載のアルミナ被覆酸化チ
タン粉末の製造方法。 ６、溶剤が水、水溶性有機溶剤および疎水性有機溶剤を
含む水溶性有機溶剤よりなる群から選ばれた少なくとも
一つの液体である請求項１記載のアルミナ被覆酸化チタ
ン粉末の製造方法。[Claims] 1. A mixture of titanium oxide powder with a total chlorine content and sulfur content of 0.05% by weight or less and a sol containing high-purity aluminum hydroxide made from aluminum alcoholate is dispersed in a solvent. In this state, the sol component on the surface of the titanium oxide particles is changed to a gel component by keeping the temperature at 60 to 300°C, and then the excess sol component, solvent, or both are removed and the resulting powder is fired at 300 to 1000°C. A method for producing alumina-coated titanium oxide powder, characterized in that: 2. The method for producing an alumina-coated titanium oxide powder according to claim 1, wherein the titanium oxide is rutile titanium oxide, anatase titanium oxide, or a mixture thereof. 3. The method for producing an alumina-coated titanium oxide powder according to claim 1, wherein the aluminum alcoholate is trialkoxyaluminum containing an alkyl group having 1 to 4 carbon atoms. 4. The alumina-coated titanium oxide powder according to claim 1, wherein the sol containing high-purity aluminum hydroxide contains 1 to 30% by weight of alumina and substantially contains no chlorine, sulfur or alkali metal. Production method. 5. The sol according to claim 1 or 4, wherein the sol containing high-purity aluminum hydroxide contains any one of silica sol, zirconia sol, or thickening inhibitor, or a mixture of two or more thereof, as a secondary component, if necessary. A method for producing alumina-coated titanium oxide powder. 6. The method for producing alumina-coated titanium oxide powder according to claim 1, wherein the solvent is at least one liquid selected from the group consisting of water, water-soluble organic solvents, and water-soluble organic solvents including hydrophobic organic solvents.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63164594A JPH0214819A (en) | 1988-06-30 | 1988-06-30 | Production of alumina-coated titanium oxide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63164594A JPH0214819A (en) | 1988-06-30 | 1988-06-30 | Production of alumina-coated titanium oxide powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0214819A true JPH0214819A (en) | 1990-01-18 |
Family
ID=15796148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63164594A Pending JPH0214819A (en) | 1988-06-30 | 1988-06-30 | Production of alumina-coated titanium oxide powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0214819A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5156889A (en) * | 1990-03-12 | 1992-10-20 | The Mearl Corporation | Process for stabilizing metal oxide-coated mica pigments against light and moisture |
| WO1996041840A1 (en) * | 1995-06-08 | 1996-12-27 | Institut für Neue Materialien Gemeinnützige GmbH | Coated inorganic pigments, process for their production and their use |
| JP2009019320A (en) * | 2007-06-11 | 2009-01-29 | Sakata Corp | Water-based pre-coating agent for offset printing |
-
1988
- 1988-06-30 JP JP63164594A patent/JPH0214819A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5156889A (en) * | 1990-03-12 | 1992-10-20 | The Mearl Corporation | Process for stabilizing metal oxide-coated mica pigments against light and moisture |
| WO1996041840A1 (en) * | 1995-06-08 | 1996-12-27 | Institut für Neue Materialien Gemeinnützige GmbH | Coated inorganic pigments, process for their production and their use |
| JP2009019320A (en) * | 2007-06-11 | 2009-01-29 | Sakata Corp | Water-based pre-coating agent for offset printing |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2875993B2 (en) | Anatase dispersion and method for producing the same | |
| CN110436508B (en) | Preparation method and application of flaky nano copper oxide | |
| JPH06207118A (en) | White conductive titanium dioxide powder and its production | |
| JP6449903B2 (en) | Plate-like aluminum oxide and method for producing the same | |
| US4757037A (en) | Neodymium titanate and barium neodymium titanate, processes for their preparation, and their applications in ceramic compositions | |
| US4695439A (en) | Yttrium oxide stabilized zirconium oxide | |
| JPH0214819A (en) | Production of alumina-coated titanium oxide powder | |
| CN107108372A (en) | The manufacture method of β eucryptite particulates | |
| JPS61106414A (en) | Fine powder of electroconductive titanium oxide of low oxidation state and its preparation | |
| US5246623A (en) | Method for the preparation of electrically conductive tin-iv-oxide of fine-particle size and the use of tin-iv-oxide as filler and pigment | |
| US3798045A (en) | Silica encapsulated lead chromate pigment of the primrose yellow shade | |
| US20190153613A1 (en) | Method for the production of single crystalline tio2 flakes | |
| JP3490012B2 (en) | Method for producing crystalline titanium oxide particle dispersion liquid | |
| JPH06256682A (en) | Pearlescent pigment and its preparation | |
| JP6441366B2 (en) | Method for producing single crystal MgTiO3 flakes | |
| CN114671460A (en) | Method for removing impurities from industrial metatitanic acid in sulfuric acid method titanium dioxide short-flow process | |
| JP2528462B2 (en) | Method for producing sodium hexatitanate fine particle powder | |
| JP2003192348A (en) | Titanium oxide sol dispersed in organic solvent, and its production method | |
| CN101941728B (en) | Method for preparing sheet alumina | |
| US2988424A (en) | Process for controlling the density of a laminar form of alumina | |
| JPH09263951A (en) | Production of low core loss grain oriented silicon steel sheet | |
| JPH04359082A (en) | Hydrous lipophilic phyllosilicate | |
| CN109179441A (en) | A kind of high-brightness sericite powder of modification | |
| JPH046102A (en) | Production of zirconium nitride powder | |
| JPH02149424A (en) | White color conductive material and its production |