JPH04193712A - Transition alumina and its production - Google Patents
Transition alumina and its productionInfo
- Publication number
- JPH04193712A JPH04193712A JP2324960A JP32496090A JPH04193712A JP H04193712 A JPH04193712 A JP H04193712A JP 2324960 A JP2324960 A JP 2324960A JP 32496090 A JP32496090 A JP 32496090A JP H04193712 A JPH04193712 A JP H04193712A
- Authority
- JP
- Japan
- Prior art keywords
- water
- alumina
- aluminum hydroxide
- transition alumina
- aluminum
- 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
- 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 46
- 230000007704 transition Effects 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011164 primary particle Substances 0.000 claims abstract description 18
- 239000000839 emulsion Substances 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- -1 aluminum alkoxide Chemical class 0.000 claims abstract description 9
- 238000010304 firing Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 23
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 229910001593 boehmite Inorganic materials 0.000 claims description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 9
- 239000007762 w/o emulsion Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000009827 uniform distribution Methods 0.000 abstract description 6
- 239000000945 filler Substances 0.000 abstract description 5
- 239000003082 abrasive agent Substances 0.000 abstract description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 150000004703 alkoxides Chemical class 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 3
- 229920000053 polysorbate 80 Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000011124 aluminium ammonium sulphate Nutrition 0.000 description 2
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229960005235 piperonyl butoxide Drugs 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、研磨材や各種樹脂への充填材として優れた遷
移アルミナおよびその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to transition alumina, which is excellent as a filler for abrasives and various resins, and a method for producing the same.
近年、アルミナの用途として磁気ディスクの研磨剤ある
いはビデオテープの充填剤の用途等が注目されるように
なってきた。これらの用途に対し、アルミナの特性とし
て適切な硬度や熱伝導性の他に、−成粒子が微細で球状
に近く、かつ均一な分布を有するものが望まれている。In recent years, alumina has been attracting attention as an abrasive for magnetic disks and a filler for video tapes. For these uses, in addition to appropriate hardness and thermal conductivity, alumina is desired to have fine particles, nearly spherical shape, and uniform distribution.
このため種々の製造方法が検討されてきた。For this reason, various manufacturing methods have been studied.
塩化アルミニウムの気相分解による方法では、遷移アル
ミナとして非晶質成分を含む、主としてγ−アルミナか
らなる遷移アルミナ、あるいはδ−アルミナからなる遷
移アルミナが報告されている（Ｋａｕｔｓｃｈｕｋ ｕ
ｎｄ Ｇｕｍｍｉ、Ｋｕｎｓｔｓｔｏｆｆｅ、２０，１
０．第５７８〜５８６頁（１９６７年））、 （Ａｎｇ
ｅｗａｎｄｔｅ Ｃｈｅｍｉｅ。In the gas phase decomposition method of aluminum chloride, transition alumina containing an amorphous component and mainly consisting of γ-alumina or δ-alumina has been reported (Kautschuk U.
nd Gummi, Kunststoffe, 20,1
0. pp. 578-586 (1967)), (Ang
ewandte Chemie.
７２（１９／２）、第７４４〜７５０頁（１９６０年）
）。72 (19/2), pp. 744-750 (1960)
).
この方法では、ＢＥＴが約１００ｍ２７ｇで平均粒径が
約２０ｎｍの比較的均一な粒度分布を有するアルミナが
得られるが、結晶相の制御や一次粒子径の制御が困難で
ある。This method yields alumina having a relatively uniform particle size distribution with a BET of about 100 m27 g and an average particle size of about 20 nm, but it is difficult to control the crystal phase and primary particle size.
また、アンモニウムミョウバン熱分解法では気相法と同
様に直接に遷移アルミナが得られる。Furthermore, in the ammonium alum pyrolysis method, transition alumina can be obtained directly as in the gas phase method.
液相法としては、アルコキシドの加水分解により水酸化
アルミニウムを合成し、これを焼成することにより遷移
アルミナを経てα−アルミナを製造することが従来より
知られている。As a liquid phase method, it has been conventionally known to synthesize aluminum hydroxide by hydrolyzing an alkoxide, and to produce α-alumina via transition alumina by firing the aluminum hydroxide.
たとえば、水酸化アルミニウムであるベーマイトを加熱
することにより、約５００℃でγ−アルミナが生成し、
さらに加熱することによりδ→θ→α−アルミナへと変
化する。この合成法では、微細な水酸化アルミニウムを
経由することにより一次粒子の大きさや結晶相の制御は
可能であると考えられている。このため、アルコキシド
の加水分解法において種々の試みかなされてきた。その
結果、アルコキシドや溶媒の種類および加水分解等の条
件により、生成する水酸化アルミニウムの構造や形態か
変化することが判明した。For example, by heating boehmite, which is aluminum hydroxide, γ-alumina is produced at about 500°C.
By further heating, it changes from δ→θ→α-alumina. In this synthesis method, it is thought that it is possible to control the size and crystal phase of the primary particles by using fine aluminum hydroxide. For this reason, various attempts have been made in methods for hydrolyzing alkoxides. As a result, it was found that the structure and form of the aluminum hydroxide produced changes depending on the type of alkoxide, solvent, and hydrolysis conditions.
Ｙｏｌｄａｓは、加水分解の条件等により水酸化アルミ
ニウムの形態や大きさが板状や針状、あるいは不規則形
状等のように変化すること、また、加水分解により合成
したゲルに塩酸を添加し解膠することにより、５〜３５
ｎｍの球状のゲルが得られること等を開示している（Ａ
ｍｅｒｉｃａｎ Ｃｅｒａｍｉｃ ５ｏｃｉｔｙＢｕｌ
ｌｅｔｉｎ、５４．Ｎｏ３（１９７５）、第２８９〜２
９０頁）。Yoldas is based on the fact that the shape and size of aluminum hydroxide changes depending on the hydrolysis conditions, such as plate-like, needle-like, or irregular shapes, and that hydrochloric acid is added to the gel synthesized by hydrolysis. By glueing, 5 to 35
It is disclosed that a spherical gel of nm size can be obtained (A
merican Ceramic 5ocityBul
Letin, 54. No. 3 (1975), No. 289-2
90 pages).
塩化アルミニウムの気相分解法では、水酸化アルミニウ
ムの状態を経ずして遷移アルミナが直接生成される。し
たかって、粉末粒子の硬度が主として支配される結晶相
の制御や一次粒子径の制御が困難であった。In the vapor phase decomposition method of aluminum chloride, transition alumina is directly produced without passing through the state of aluminum hydroxide. Therefore, it has been difficult to control the crystal phase, which mainly controls the hardness of powder particles, and the primary particle diameter.
アンモニウムミョウバン熱分解法では、ミョウバンは加
熱すると約８０℃で自己の結晶水に溶解し、さらに加熱
すると、約２２０℃で結晶水が抜け、約５３０℃で硫安
相当成分か離脱、約９００ ’ＣでＳＯ３が離脱し遷移
アルミナになる。遷移アルミナを得るには約９００°Ｃ
まで昇温しなければならない。このため、微細な一次粒
子を得ることは困難であった。In the ammonium alum pyrolysis method, when alum is heated, it dissolves in its own water of crystallization at about 80°C, and when heated further, the water of crystallization is removed at about 220°C, and the component equivalent to ammonium sulfate is separated at about 530°C, and at about 900'C. SO3 separates and becomes transitional alumina. Approximately 900°C to obtain transition alumina
The temperature must be raised to For this reason, it has been difficult to obtain fine primary particles.
したがって、これらの方法では一次粒子が微細で球状の
アルミナを製造することは難しいとされている。Therefore, it is said that it is difficult to produce alumina whose primary particles are fine and spherical using these methods.
一方、アルコキシドの加水分解法は微粒の水酸−３＝
化アルミニウムを経由するため、一次粒子の大きさや結
晶相の制御の可能性があるとされている。On the other hand, since the alkoxide hydrolysis method uses fine particles of aluminum hydroxide, it is said that it is possible to control the size and crystalline phase of the primary particles.
しかし、従来の技術では加水分解反応が速いため、水酸
化アルミニウムの一次粒子の大きさや形状、さらに一次
粒子の凝集状態の制御が困難であった。However, since the hydrolysis reaction is fast in the conventional technology, it is difficult to control the size and shape of the primary particles of aluminum hydroxide, as well as the state of aggregation of the primary particles.
たとえば、Ｙｏｌｄａｓはアルコキシドや溶媒の種類お
よび加水分解等の条件により、生成する水酸化アルミニ
ウムの構造や形態が変化することを報告している。しか
し、これらは表面コーティング用ゾルの合成が目的であ
り、水酸化アルミニウムやアルミナ粉末に関するもので
はなかった。For example, Yoldas reported that the structure and form of aluminum hydroxide to be produced change depending on the type of alkoxide, solvent, and conditions of hydrolysis. However, these efforts were aimed at synthesizing sol for surface coating, and were not concerned with aluminum hydroxide or alumina powder.
また、単分散した１００〜４００ｎｍのアモルファスの
水酸化アルミニウム（先進材料科学技術研究会第１回年
次総会学術シンポジウム予稿集（１９８９）、第３１頁
）や、平均粒径が１２〜２０ｎｍのアモルファス硫酸ア
ルミニウム、または結晶質の硫酸アルミニウムを経由し
たγ−アルミナやθ−アルミナ、θ−アルミナ等が報告
されている（第４２回コロイドおよび界面化学問論会要
旨集、（＋９８９）、第４１０頁）。In addition, monodispersed amorphous aluminum hydroxide with a particle size of 100 to 400 nm (Proceedings of the 1st Annual Meeting of the Advanced Materials Science and Technology Research Society Academic Symposium (1989), p. 31), and amorphous aluminum hydroxide with an average particle size of 12 to 20 nm. γ-alumina, θ-alumina, θ-alumina, etc. via aluminum sulfate or crystalline aluminum sulfate have been reported (Proceedings of the 42nd Colloid and Interface Chemistry Conference, (+989), p. 410) ).
単分散した１００〜４００ｎｍのアモルファスの水酸化
アルミニウムは、本発明で目的としている１〜３０ｎｍ
の粒径よりも大きく、平均粒径が１２〜２０ｎｍのアモ
ルファス硫酸アルミニウム、または結晶質の硫酸アルミ
ニウムを経由したγ−アルミナやθ−アルミナ、θ−ア
ルミナ等の遷移アルミナを得るには、焼成温度がかなら
高温である１０００°Ｃまで昇温しなくてはならないた
め、微細なものが得られない。Monodispersed amorphous aluminum hydroxide with a diameter of 100 to 400 nm is 1 to 30 nm, which is the objective of the present invention.
In order to obtain amorphous aluminum sulfate with an average particle size of 12 to 20 nm, or transition alumina such as γ-alumina, θ-alumina, θ-alumina, etc. via crystalline aluminum sulfate, the calcination temperature is In the case of Gakana, the temperature must be raised to a high temperature of 1000°C, so fine particles cannot be obtained.
エマルジョンを用いた無機粉末の合成も検討されている
。たとえば、硝酸イツトリウムのエマルジョンからの酸
化イツトリウムの合成（Ａｄｖａｎｃｅｓｉｎ Ｃｅｒ
ａｍｉｃｓ、ｖｏｌ、２１：Ｃｅｒａｍｉｃ Ｐｏｗｄ
ｅｒ ５ｃｉｅｎｃｅ（１９８６）、第５７〜６７頁）
、や水のｗ ／ ０エマルジヨンを金属アルコキシドと
接触することによる金属酸化物の製造方法（特表平２−
５０１．３８３）が知られている。しかし、前者はアル
ミナに関するものでなく、後者は支持体上への金属酸化
膜の形成が目的であり、粉末の製造方法に関するもので
はない。The synthesis of inorganic powders using emulsions is also being considered. For example, the synthesis of yttrium oxide from an emulsion of yttrium nitrate (Advancesin Cer
amics, vol, 21: Ceramic Powd
er 5science (1986), pp. 57-67)
A method for producing metal oxides by contacting a w/0 emulsion of , or water with a metal alkoxide
501.383) is known. However, the former does not relate to alumina, and the latter aims to form a metal oxide film on a support, and does not relate to a method for producing powder.
以上のことから、適切な硬度や熱伝導性の他に一次粒子
が微細な球状で、かつ均一な分布を有する遷移アルミナ
は、従来の方法では満足なものが得られなかった。From the above, it has not been possible to obtain satisfactory transition alumina, which has appropriate hardness and thermal conductivity, as well as primary particles having a fine spherical shape and uniform distribution, by conventional methods.
かかる問題点を解決するために鋭意検討を行なった結果
、平均一次粒子径が微細な球状の水酸化アルミニウムを
焼成することにより遷移アルミナを得て本発明を完成し
た。As a result of intensive studies to solve these problems, the present invention was completed by obtaining transition alumina by firing spherical aluminum hydroxide having a fine average primary particle size.
すなわち、本発明はアモルファス状ベーマイトで、平均
一次粒子径が１〜３０ｎｍである球状の水酸化アルミニ
ウムを焼成してなる遷移アルミナおよびその製造方法に
関するものである。That is, the present invention relates to transition alumina made by firing spherical aluminum hydroxide, which is amorphous boehmite and has an average primary particle size of 1 to 30 nm, and a method for producing the same.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明において得られる水酸化アルミニウムは、針状粒
子を含まない球状のアモルファス状ベーマイトで、その
平均一次粒子径は１〜３０ｎｍである。The aluminum hydroxide obtained in the present invention is spherical amorphous boehmite containing no needle particles, and its average primary particle diameter is 1 to 30 nm.
該水酸化アルミニウムは、ｗ／ｏエマルジョンの形態を
有する水とアルミニウムアルコキシドの加水分解により
得ることができる。The aluminum hydroxide can be obtained by hydrolysis of aluminum alkoxide with water in the form of a w/o emulsion.
水のｗ／ｏエマルジョンの作製方法は、通常は水と疎水
性溶媒さらに非イオン性界面活性剤の混合溶液をホモジ
ナイザーなどにより乳化処理を施すことにより得られる
。A w/o emulsion of water is usually prepared by emulsifying a mixed solution of water, a hydrophobic solvent, and a nonionic surfactant using a homogenizer or the like.
溶媒としては、シクロヘキサン、トルエン、ベンゼン、
四塩化炭素、■、２ジクロロエタン、イソオクタン、分
散剤としてはノニポール４０（三洋化成工業■製）、ス
パン６０（和光紬薬工業■製）、トウイーン８０（和光
純薬玉業■製）等を用いることができる。As a solvent, cyclohexane, toluene, benzene,
Carbon tetrachloride, dichloroethane, isooctane, and dispersants such as Nonipol 40 (manufactured by Sanyo Chemical Industries, Ltd.), Span 60 (manufactured by Wako Tsumugi Kogyo, Ltd.), Tween 80 (manufactured by Wako Pure Yakugyo, Ltd.), etc. may be used. I can do it.
水のｗ／ｏエマルジョンの粒径が１０μｍ以上の場合は
粗大凝集粒の低減の効果が小さく、針状の水酸化アルミ
ニウムが生成するので、好ましくは１０μｍ以下、さら
に好ましくは５μｍ以下が適当である。If the particle size of the water w/o emulsion is 10 μm or more, the effect of reducing coarse agglomerated particles will be small and acicular aluminum hydroxide will be produced, so it is preferably 10 μm or less, more preferably 5 μm or less. .
アルミニウムアルコキシドは、通常、メトキシド、エト
キシド、ｉ−プロポキシド、ｎ−プロポキシド、ｎ−ブ
トキシド、ｉ−ブトキシド、５ｅＣ−ブトキシド等が使
用できる。溶媒としては、分散剤の溶解度には関係なく
アルミニウムアルコキシドを溶解するものであれば使用
でき、たとえば、エタノール、イソプロピルアルコール
、ベンゼン、シクロヘキサン、トルエン、クロロホルム
、四塩化炭素等を用いることができる。As the aluminum alkoxide, methoxide, ethoxide, i-propoxide, n-propoxide, n-butoxide, i-butoxide, 5eC-butoxide, etc. can usually be used. Any solvent that can dissolve the aluminum alkoxide regardless of the solubility of the dispersant can be used, such as ethanol, isopropyl alcohol, benzene, cyclohexane, toluene, chloroform, carbon tetrachloride, etc.
加水分解は、アルコキシド溶液に水のＷ ／ Ｏエマル
ジョンを滴下、混合することにより行った。Hydrolysis was performed by dropping a W/O emulsion of water into the alkoxide solution and mixing.
たとえば、噴霧法など他の方法で混合を行っても問題は
ない。For example, there is no problem in mixing by other methods such as a spraying method.
このようにして得た生成物を乾燥して水酸化アルミニウ
ムを得た。The product thus obtained was dried to obtain aluminum hydroxide.
本発明による製造方法で得られる水酸化アルミニウムの
一次粒子は、針状の粒子を含まず、球形で平均粒径１〜
３０ｎｍの均一な粒度分布を示し、その結晶構造はアモ
ルファス状ベーマイトである。The primary particles of aluminum hydroxide obtained by the production method according to the present invention do not contain acicular particles, are spherical, and have an average particle size of 1 to 1.
It shows a uniform particle size distribution of 30 nm, and its crystal structure is amorphous boehmite.
従来報告されているベーマイトは、針状あるいは繊維状
となる場合が多いが、本発明の製造方法によれば、針状
の粒子を含まず、球形で均一な粒度分布を示し、結晶構
造がアモルファス状ベーマイトである水酸化アルミニウ
ムが得られるが、その合成メカニズムは十分明らかでは
ない。Conventionally reported boehmite is often acicular or fibrous, but according to the production method of the present invention, it does not contain acicular particles, has a spherical and uniform particle size distribution, and has an amorphous crystal structure. Aluminum hydroxide, a type of boehmite, can be obtained, but its synthesis mechanism is not fully clear.
本発明の製造方法では、水のｗ／ｏエマルジョンの界面
に存在する界面活性剤により、加水分解が抑制されベー
マイトの生成速度が遅くなる、あるいはアルコキシドと
界面活性剤の反応によるものと推定されるが明らかでは
ない。In the production method of the present invention, it is presumed that the surfactant present at the interface of the water w/o emulsion suppresses hydrolysis and slows down the boehmite production rate, or that it is due to the reaction between the alkoxide and the surfactant. is not clear.
さらに、本発明の製造方法で得られた水酸化アルミニウ
ム粉末を５００〜１０００°Ｃの大気中で焼成すること
により、針状粒子を含まない球形の遷移アルミナを得る
ことができる。その平均粒径は１〜３０ｎｍで、均一な
分布を有する。Further, by firing the aluminum hydroxide powder obtained by the production method of the present invention in the atmosphere at 500 to 1000°C, spherical transition alumina containing no acicular particles can be obtained. Its average particle size is 1-30 nm and has a uniform distribution.
したがって、この遷移アルミナは精密研磨材や樹脂フィ
ルムの充填材として最適である。Therefore, this transitional alumina is most suitable as a filler for precision abrasives and resin films.
従来の針状のベーマイトの場合、焼成温度を高くするこ
とにより、針状粒子は結晶転移のため球状化するが、焼
成温度を高くする必要があり、針状粒子を含まないγ−
アルミナやδ−アルミナを得ることが困難であったが、
本発明により ５００〜１０００℃の焼成温度領域で針
状粒子の無い遷移アルミナを製造することができる。In the case of conventional acicular boehmite, by increasing the firing temperature, the acicular particles become spherical due to crystal transition, but it is necessary to increase the calcination temperature, and γ-
Although it was difficult to obtain alumina and δ-alumina,
According to the present invention, transition alumina free of acicular particles can be produced in the calcination temperature range of 500 to 1000°C.
本発明で得られた遷移アルミナは、一次粒子が微細な球
状でかつ均一な分布を有し、精密研磨材やビデオテープ
の充填材として有用なものである。The transition alumina obtained according to the present invention has primary particles having a fine spherical shape and uniform distribution, and is useful as a precision abrasive or a filler for videotapes.
以下、実施例により本発明を具体的に説明するが、本発
明はこれらに限定されるものではない。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.
なお、本発明における各種測定は以下の方法で行った。In addition, various measurements in the present invention were performed by the following methods.
粉末およびエマルジョン粒度分布
：マスターサイザー（マルバーン社（米国）１）一次粒
子形状および粒径
：透過型電子顕微鏡（日本電子■製４０００ＦＸ）結晶
相
＝Ｘ線回折（（掬すガク製ＲＡＤ−Ｃ）実施例１〜７
水はイオン交換水を用い、さらに疎水性溶媒と界面活性
剤を加えた混合溶液を第１表に示す所定の濃度で調整し
た。Powder and emulsion particle size distribution: Mastersizer (Malvern Co., Ltd. (USA) 1) Primary particle shape and particle size: Transmission electron microscope (4000FX manufactured by JEOL) Crystal phase = X-ray diffraction (RAD-C manufactured by Kikisu Gaku) Examples 1 to 7 Ion-exchanged water was used as water, and a mixed solution containing a hydrophobic solvent and a surfactant was prepared at a predetermined concentration shown in Table 1.
疎水性溶媒としてはシクロヘキサン（実施例１〜７）、
界面活性剤としてはノニポール４０（三洋化成工業■製
）単独で（実施例６．７）、またはスパン６０（和光純
薬工業（株制）とトウイーン８０（和光純薬玉業■製）
とを組合せて（実施例１〜５）用いた。As the hydrophobic solvent, cyclohexane (Examples 1 to 7),
As surfactants, Nonipol 40 (manufactured by Sanyo Chemical Industries, Ltd.) alone (Example 6.7), or Span 60 (manufactured by Wako Pure Chemical Industries, Ltd.) and Tween 80 (manufactured by Wako Pure Chemical Industries, Ltd.) were used.
(Examples 1 to 5) were used in combination.
スパン６０とトウイーン８０との混合比は５．０：４．
１とした。The mixing ratio of Span 60 and Tween 80 is 5.0:4.
It was set to 1.
これをホモジナイザー（シルバーソン社（米国）製）で
乳化処理し、水のｗ／ｏエマルジョンを得た。エマルジ
ョンの粒径は０．５〜５μｍであった。This was emulsified using a homogenizer (manufactured by Silverson Co., USA) to obtain a w/o emulsion of water. The particle size of the emulsion was 0.5-5 μm.
アルミニウムアルコキサイド溶液は、市販のアルミニウ
ムイソプロポキシドを用い、溶媒としてはシクロヘキサ
ン（実施例２〜５）またはイソプロピルアルコール（実
施例１．６．７）を用いた。Commercially available aluminum isopropoxide was used as the aluminum alkoxide solution, and cyclohexane (Examples 2 to 5) or isopropyl alcohol (Example 1.6.7) was used as the solvent.
加水分解反応は、セパラブルフラスコを用いアルミニウ
ムアルコキサイド溶液に水のｗ１０エマルジョンを滴下
、混合することにより行った。The hydrolysis reaction was carried out by dropping a W10 emulsion of water into the aluminum alkoxide solution and mixing it using a separable flask.
反応温度は７５〜８５°Ｃ１水／アルミニウムイソプロ
ポキシドの比は化学量論比であればよいが、多少ずれて
も問題ない。The reaction temperature is 75 to 85° C. The water/aluminum isopropoxide ratio may be a stoichiometric ratio, but there is no problem even if the ratio is slightly different.
加水分解後、生成物を遠心分離機で溶媒から分離し、セ
パラブルフラスコ中で乾燥して（最初は８０℃、最終的
に１０５°Ｃになるまで乾燥した）水酸化アルミニウム
を得た。After hydrolysis, the product was separated from the solvent in a centrifuge and dried in a separable flask (initially at 80°C and finally at 105°C) to obtain aluminum hydroxide.
該水酸化アルミニウムを、電気炉中８００℃で焼成して
球形の遷移アルミナを得た。The aluminum hydroxide was fired at 800° C. in an electric furnace to obtain spherical transition alumina.
得られた水酸化アルミニウムおよび遷移アルミナの特性
を第１表に示す。Table 1 shows the properties of the aluminum hydroxide and transition alumina obtained.
比較例１〜３
比較例１．２は加水分解に必要な水をエマルジョンにせ
ずイソプロパツールとの混合溶液として添加した以外は
比較例１は実施例５と同様に、また比較例２は実施例２
と同様にして針状の遷移アルミナを得た。Comparative Examples 1 to 3 In Comparative Examples 1 and 2, Comparative Example 1 was the same as Example 5, and Comparative Example 2 was the same as Example 5, except that the water required for hydrolysis was added as a mixed solution with isopropanol instead of being made into an emulsion. Example 2
Acicular transition alumina was obtained in the same manner as above.
比較例３では水のｗ／ｏエマルジョンの粒径を１２μｍ
にした以外は実施例４と同様にして針状のγ−アルミナ
を得た。In Comparative Example 3, the particle size of the water w/o emulsion was 12 μm.
Acicular γ-alumina was obtained in the same manner as in Example 4, except that .
得られた水酸化アルミニウムおよび遷移アルミナの特性
を第１表に示す。Table 1 shows the properties of the aluminum hydroxide and transition alumina obtained.
Claims (3)
１〜３０ｎｍである球状の水酸化アルミニウムを焼成し
てなる遷移アルミナ。(1) Transition alumina made by firing spherical aluminum hydroxide, which is amorphous boehmite and has an average primary particle size of 1 to 30 nm.
水酸化アルミニウムを製造する工程において、水をｗ／
ｏエマルジョンにして反応させて得た球状の水酸化アル
ミニウムを用いて焼成することを特徴とする遷移アルミ
ナの製造方法。(2) In the process of producing aluminum hydroxide by reacting aluminum alkoxide with water, water is
o A method for producing transition alumina, which comprises firing using spherical aluminum hydroxide obtained by reaction in the form of an emulsion.
粒径が１０μｍ以下であることを特徴とする請求項２記
載の遷移アルミナの製造方法。(3) The method for producing transition alumina according to claim 2, wherein the average particle size of the w/o emulsion of water to be subjected to hydrolysis is 10 μm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2324960A JPH04193712A (en) | 1990-11-26 | 1990-11-26 | Transition alumina and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2324960A JPH04193712A (en) | 1990-11-26 | 1990-11-26 | Transition alumina and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04193712A true JPH04193712A (en) | 1992-07-13 |
Family
ID=18171551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2324960A Pending JPH04193712A (en) | 1990-11-26 | 1990-11-26 | Transition alumina and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04193712A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11268911A (en) * | 1998-01-08 | 1999-10-05 | Nissan Chem Ind Ltd | Alumina powder, its production, and composition for polishing |
| WO2001047812A1 (en) * | 1999-12-27 | 2001-07-05 | Showa Denko K.K. | Alumina particles, method for producing the same, composition comprising the same, and alumina slurry for polishing |
| JP2002064272A (en) * | 2000-08-16 | 2002-02-28 | Ibiden Co Ltd | Multilayered printed wiring board and manufacturing method therefor |
| KR100457068B1 (en) * | 2002-01-16 | 2004-11-10 | 함영민 | Process for preparation of alumina powder by using the w/o emulsion method |
| US7067105B2 (en) | 1999-12-27 | 2006-06-27 | Showa Denko K.K. | Alumina particles, production process thereof, composition comprising the particles and alumina slurry for polishing |
| WO2007047547A2 (en) * | 2005-10-14 | 2007-04-26 | Saint-Gobain Ceramics & Plastics, Inc. | Abrasive particulate material, and method of planarizing a workpiece using the abrasive particulate material |
| CN116059985A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Spherical alumina carrier and its synthesis process |
-
1990
- 1990-11-26 JP JP2324960A patent/JPH04193712A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11268911A (en) * | 1998-01-08 | 1999-10-05 | Nissan Chem Ind Ltd | Alumina powder, its production, and composition for polishing |
| WO2001047812A1 (en) * | 1999-12-27 | 2001-07-05 | Showa Denko K.K. | Alumina particles, method for producing the same, composition comprising the same, and alumina slurry for polishing |
| US7067105B2 (en) | 1999-12-27 | 2006-06-27 | Showa Denko K.K. | Alumina particles, production process thereof, composition comprising the particles and alumina slurry for polishing |
| JP2002064272A (en) * | 2000-08-16 | 2002-02-28 | Ibiden Co Ltd | Multilayered printed wiring board and manufacturing method therefor |
| KR100457068B1 (en) * | 2002-01-16 | 2004-11-10 | 함영민 | Process for preparation of alumina powder by using the w/o emulsion method |
| WO2007047547A2 (en) * | 2005-10-14 | 2007-04-26 | Saint-Gobain Ceramics & Plastics, Inc. | Abrasive particulate material, and method of planarizing a workpiece using the abrasive particulate material |
| WO2007047547A3 (en) * | 2005-10-14 | 2007-06-14 | Saint Gobain Ceramics | Abrasive particulate material, and method of planarizing a workpiece using the abrasive particulate material |
| JP2009511719A (en) * | 2005-10-14 | 2009-03-19 | サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド | Abrasive particle material and method for planarizing a workpiece using the abrasive particle material |
| US8685123B2 (en) | 2005-10-14 | 2014-04-01 | Saint-Gobain Ceramics & Plastics, Inc. | Abrasive particulate material, and method of planarizing a workpiece using the abrasive particulate material |
| CN116059985A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Spherical alumina carrier and its synthesis process |
| CN116059985B (en) * | 2021-10-29 | 2024-05-07 | 中国石油化工股份有限公司 | Spherical alumina carrier and its synthesis process |
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