JPH02296711A - Spherical silica particle and its production - Google Patents
Spherical silica particle and its productionInfo
- Publication number
- JPH02296711A JPH02296711A JP11909289A JP11909289A JPH02296711A JP H02296711 A JPH02296711 A JP H02296711A JP 11909289 A JP11909289 A JP 11909289A JP 11909289 A JP11909289 A JP 11909289A JP H02296711 A JPH02296711 A JP H02296711A
- Authority
- JP
- Japan
- Prior art keywords
- flame
- silica
- particle size
- spherical silica
- fine particles
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 55
- 239000002245 particle Substances 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000010419 fine particle Substances 0.000 claims description 28
- 239000000945 filler Substances 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011148 porous material Substances 0.000 description 12
- 230000007062 hydrolysis Effects 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002002 slurry Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000000635 electron micrograph Methods 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/181—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は球状シリカ微粒子、特にはアルコキシシランの
加水分解で得られたシリカを火炎で乾燥、無孔化してな
る、粒度分布が狭く無孔質なことからプラスチックパッ
ケージ用充填剤として有用とされる球状シリカ微粒子お
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 is made by drying spherical silica fine particles, particularly silica obtained by hydrolyzing alkoxysilane, with a flame to make it non-porous, and which has a narrow particle size distribution and is non-porous. The present invention relates to spherical silica fine particles that are useful as fillers for plastic packages due to their high quality, and a method for producing the same.
［従来の技術］
シリカの製造方法については各種の方法が知られており
、アルコキシシランを加水分解して得られるシリカは粒
度分布が狭く、高純度のものになるが、これにはアルカ
リ触媒としてアンモニアを用いたＮＨ，−Ｈ，０−アル
コール溶液中にアルコキシシラン−アルコール溶液を滴
下して粒径が０．０２〜１ μｍのシリカを得る方法（
Ｊ、 Ｃｏ１１ｏｉｄ ＩｎｔｅｒｆａｃｅＳｃｉ、
２６．６２（１９６８）参照］、塩酸などの酸性触媒の
存在下に水および／またはアルコール溶液をアルコキシ
シランに添加して粒径１〜５００μｍのシリカを得る方
法（特開昭６２−１３８３３５号公報参照）が）是案さ
れている。[Prior Art] Various methods are known for producing silica, and the silica obtained by hydrolyzing alkoxysilane has a narrow particle size distribution and is highly pure. A method of obtaining silica with a particle size of 0.02 to 1 μm by dropping an alkoxysilane-alcohol solution into an NH, -H, 0-alcohol solution using ammonia (
J, Co11oid Interface Sci.
26.62 (1968)], a method of obtaining silica with a particle size of 1 to 500 μm by adding water and/or alcohol solution to alkoxysilane in the presence of an acidic catalyst such as hydrochloric acid (Japanese Patent Application Laid-open No. 138335/1982). ) is recommended.
しかし、これらの方法で得られるシリカは微細な細孔を
有するためにＢＥＴ法による比表面積が１０〜３００＋
＋＋２７ｇと非常に大きいので、これを例えばＩＣなど
のプラスチックパッケージ用充填剤として使用すると、
その細孔内の空気を除去できず、パッケージの熱伝導度
が低下したり、またこの細孔を無孔化するためにスプレ
ードライヤーや抵抗加熱炉で加熱すると粒子同志が融着
したり、焼結を起こすという不利がある。However, since the silica obtained by these methods has fine pores, the specific surface area by the BET method is 10 to 300+.
++It is very large at 27g, so if you use it as a filler for plastic packages such as ICs,
If the air inside the pores cannot be removed, the thermal conductivity of the package will decrease, and if the pores are heated with a spray dryer or resistance heating furnace to make them non-porous, the particles may fuse together or burn out. It has the disadvantage of causing knots.
そのため、このシリカを無孔化する方法が検討されてお
り、これについてはシリカ微粒子をスプレードライヤー
を用いて造粒し、酸水素火炎中で溶融する方法（特開昭
６０−１３１８６８号公報参照）、シリカ微粒子含有ゾ
ルを凍結乾燥し、ついで焼成する方法（特開昭６１−２
７７５２７号公報参照）、アルコキシシランの部分加水
分解で得たシリカゾルをｒＩｆｉ霧乾燥し、ついで熱分
解する方法（特開昭６２−１７８２０８号公報参照）が
提案されている。Therefore, a method of making this silica non-porous is being considered, and for this method, silica fine particles are granulated using a spray dryer and melted in an oxyhydrogen flame (see JP-A-60-131868). , a method of freeze-drying a sol containing fine silica particles and then firing it (Japanese Patent Laid-Open No. 61-2
77527), and a method in which silica sol obtained by partial hydrolysis of alkoxysilane is subjected to rIfi mist drying and then thermally decomposed (see Japanese Patent Laid-Open No. 178208/1983).
［発明が解決しようとする課題］
しかし、シリカの無孔化のために造粒後、酸水素火炎で
溶融する方法にはスプレードライヤーで造粒すると粒度
分布が広くなるし、これを酸水素火炎で溶融すると粒子
同志が融着して得られる粒子の粒度分布がさらに広くな
り、さらには工程が長くなるという欠点があり、シリカ
ゾルを凍結乾燥し、焼成する方法には焼成工程での粒子
の融着を完全に抑えることができず、これも工程が長く
なるという不利がある。また、シリカゾルを噴霧し、熱
分解するという方法では得られる粒子の粒径が噴霧時に
おける液滴の径によって決定されるので粒度分布の広い
粒子しか得られないという欠点がある。[Problems to be Solved by the Invention] However, in order to make silica non-porous, the method of granulating it and then melting it with an oxyhydrogen flame results in a wide particle size distribution when the silica is granulated with a spray dryer. If the silica sol is melted, the particles will fuse together, resulting in a wider particle size distribution, and the process will be longer. This has the disadvantage that it is not possible to completely suppress wear, and this also lengthens the process. Furthermore, the method of spraying silica sol and thermally decomposing it has the disadvantage that only particles with a wide particle size distribution can be obtained because the particle size of the particles obtained is determined by the diameter of the droplets at the time of spraying.
なお、このシリカ微粒子の無孔化についてはアルコキシ
シランの加水分解で得られたシリカ微粒子を含む溶液を
火炎中に導入することも提案されているが、これには火
炎の熱によって粒子同志が融着することを避けることが
できないという不利があり、この解決が望まれている。In order to make the silica particles non-porous, it has been proposed to introduce a solution containing silica particles obtained by hydrolyzing alkoxysilane into a flame, but this method requires that the particles fuse together due to the heat of the flame. There is a disadvantage that it is impossible to avoid wearing clothes, so a solution to this problem is desired.
［課題を解決するための手段］
本発明はこのような不利・欠点を解決した球状シリカ微
粒子およびその製造方法に関するものであり、これは多
孔質度が１．０〜２．０であり、平均粒径が０．２〜５
．０μｍで、平均粒径の変動係数が０．１５以下である
ことを特徴とする球状微粒子シリカ、およびアルコキシ
シランを加水分解して得たシリカを火炎温度が５００〜
１，３００℃の火炎中で乾燥、無孔化してなることを特
徴とする前記球状シリカ微粒子の製造方法に関するもの
である。[Means for Solving the Problems] The present invention relates to spherical silica fine particles that solve these disadvantages and drawbacks, and a method for producing the same, which has a porosity of 1.0 to 2.0 and an average Particle size is 0.2-5
．． Spherical fine particle silica characterized by having an average particle diameter of 0 μm and a coefficient of variation of 0.15 or less, and silica obtained by hydrolyzing alkoxysilane with a flame temperature of 500 to
The present invention relates to a method for producing the spherical silica fine particles, characterized in that the spherical silica particles are dried in a flame at 1,300°C to make them non-porous.
すなわち、本発明者らは粒度分布が狭く、無孔質である
球状シリカ微粒子の製造方法について種々検討した結果
、アルコキシシランを公知の加水分解法で処理して得た
シリカを火炎処理して無孔化する際に、この火炎の温度
を余り高くせず５００〜１，３００℃のものとすればシ
リカ微粒子を融着せずに無孔化し得ることを見出し、こ
れによれば粒度分布が狭く、無孔質とされた球状シリカ
微粒子を容易に、かつ効率的に得ることができることを
確認して本発明を完成させた。That is, as a result of various studies by the present inventors on the production method of spherical silica fine particles that have a narrow particle size distribution and are non-porous, the present inventors have found that silica obtained by treating alkoxysilane with a known hydrolysis method is flame-treated to make it non-porous. It has been discovered that when forming pores, if the temperature of the flame is not too high and is set at 500 to 1,300°C, it is possible to make the silica fine particles non-porous without fusing them. According to this, the particle size distribution is narrow, The present invention was completed by confirming that nonporous spherical silica particles can be easily and efficiently obtained.
以下にこれをさらに詳述する。This will be explained in further detail below.
［作 用］
本発明の球状シリカ微粒子はアルコキシシランを加水分
解して得たシリカを火炎処理することによって得ること
ができる。[Function] The spherical silica fine particles of the present invention can be obtained by flame treating silica obtained by hydrolyzing alkoxysilane.
このアルコキシシランの加水分解は公知の方法で行えば
よい。したがってこのアルコキシシランは一般式５ｔ（
ＯＲ）ｉで示され、Ｒが炭素数１〜４のアルキル基であ
るもの、例えばテトラメトキシシラン、テトラエトキシ
シラン、テトラプロポキシシラン、テトラブトキシシラ
ンなどとすればよいが、これらのうちでは高純度化が容
易であり、安価であるテトラメトキシシラン、テトラエ
トキシシランが好ましいものとされる。Hydrolysis of this alkoxysilane may be carried out by a known method. Therefore, this alkoxysilane has the general formula 5t (
OR) i and R is an alkyl group having 1 to 4 carbon atoms, such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, among which high purity Tetramethoxysilane and tetraethoxysilane are preferred because they are easy to prepare and are inexpensive.
このアルコキシシランの加水分解はこれまでに提案され
ているいかなる方法で行なってもよく、したがってこれ
はアルカリ性触媒、酸性触媒のいずれを使用してもよい
し、この加水分解の際に添加される有機溶媒の種類、量
についても制限はない、しかし、後記する火炎処理にお
いて残漬、不純物を発生するような物質は使用すべぎで
はなく、シたがって例えばアルカリ性触媒としてＮａＯ
Ｈを使用すると火炎処理したあとにＮａが残留し、これ
が金属不純物となるのでこのようなものは使用してはな
らない。Hydrolysis of this alkoxysilane may be carried out by any method proposed so far, and therefore it may be carried out using either an alkaline catalyst or an acidic catalyst, or an organic catalyst added during this hydrolysis. There are no restrictions on the type or amount of solvent, but substances that leave residue or generate impurities during the flame treatment described later should not be used, so for example, NaO as an alkaline catalyst should not be used.
If H is used, Na will remain after flame treatment, and this will become a metal impurity, so such materials should not be used.
この加水分解により得られるシリカ球状微粒子について
は粒径が０．２μｍ以下であるとこの粒子の熱容量が小
さいために後記する火炎処理で融着してしまうし、これ
が５μｍ以上であるとその分散性の調整が難しくなるの
で、これは反応条件を調整して粒径が０．２〜５μｍの
ものとする必要があるが、この反応条件についてはこの
シリカが調整すべき粒径となるように、そのアルコキシ
シランの種類、量、添加する水の量、触媒の種類、量、
有機溶媒の種類、量をこれまで提案されている方法にし
たがって決定すればよく、例えばテトラエトキシシラン
、アンモニア、水、エタノールを用いて０．５μ田の球
状シリカを得る場合には、前記した公知例の処理によっ
てテトラエトキシシランを０．２８モル／１、アノモニ
アを０．８モル／１、水を１２．５モル／ＪＺとすれば
よい。If the particle size of the silica spherical fine particles obtained by this hydrolysis is 0.2 μm or less, the particles will have a small heat capacity and will be fused during the flame treatment described later, whereas if the particle size is 5 μm or more, the dispersibility will be poor. This makes it difficult to adjust the particle size of silica, so it is necessary to adjust the reaction conditions so that the particle size is 0.2 to 5 μm. The type and amount of the alkoxysilane, the amount of water added, the type and amount of the catalyst,
The type and amount of the organic solvent may be determined according to the method proposed so far. For example, when obtaining 0.5 μm spherical silica using tetraethoxysilane, ammonia, water, and ethanol, the above-mentioned known method can be used. By the treatment in the example, the amount of tetraethoxysilane may be 0.28 mol/1, the amount of anomonia may be 0.8 mol/1, and the amount of water may be 12.5 mol/JZ.
このようにして得られたシリカスラリーは、ついで火炎
処理によって無孔化するのであるが、これはシリカスラ
リーを火炎中に噴霧して処理すればよい。しかし、この
火炎処理に当っては火炎の温度が５００℃以下では無孔
化が完全に終了せず、しかもスラリー中の有機溶剤の不
完全燃焼によってシリカ中に微量の炭素分が残留するこ
とになり、１，３００℃以上とするとシリカ粒子同志が
融着して分散性のよいシリカ球を得ることができなくな
るので、これは５００〜１，３００℃の範囲とする必要
がある。この火炎温度はフィードされた可燃性成分（可
燃性ガス、スラリー中の有機溶媒など）の燃焼により発
生する熱量と、これらを顕熱、潜熱として吸収するイナ
ート成分の量により決定されるため、これら可燃ガス、
スラリー イナートのフィード量により調整すればよい
、この火炎は酸水素炎でもメタン−酸素炎であってもよ
く、ここに使用する酸素ガスは必要量の７０％未満とす
るとスラリー中の有機溶媒、可燃性ガスの不完全燃焼を
招くので７０％以上とすることが必要とされるが、この
燃焼ガスに窒素、ヘリウム、水などの不活性成分を添加
することは火炎温度を調整することから有用とされる。The silica slurry thus obtained is then rendered non-porous by flame treatment, which can be done by spraying the silica slurry into a flame. However, in this flame treatment, if the flame temperature is below 500°C, the process of making the silica non-porous will not be completed completely, and furthermore, a trace amount of carbon will remain in the silica due to incomplete combustion of the organic solvent in the slurry. If the temperature is 1,300°C or higher, the silica particles will fuse together, making it impossible to obtain silica spheres with good dispersibility. Therefore, the temperature needs to be in the range of 500 to 1,300°C. This flame temperature is determined by the amount of heat generated by the combustion of the fed combustible components (combustible gas, organic solvent in the slurry, etc.) and the amount of inert components that absorb these as sensible heat and latent heat. combustible gas,
This flame can be adjusted by adjusting the feed rate of the slurry inert. This flame may be an oxyhydrogen flame or a methane-oxygen flame. If the oxygen gas used here is less than 70% of the required amount, the organic solvent in the slurry However, adding inert components such as nitrogen, helium, and water to this combustion gas is useful because it adjusts the flame temperature. be done.
この火炎中へのシリカスラリーの噴霧は液体噴霧、超音
波噴霧など従来公知の方法で行えばよく、火炎中に噴霧
された液滴は火炎により瞬時に乾燥され、これに含有さ
れていた有機溶媒は燃焼するので、上記した加水分解で
得られた多孔質のシリカはこの燃焼熱によって無孔化さ
れて容易に、かつ効率よく無孔化された球状シリカ微粒
子となる。Spraying of the silica slurry into the flame can be carried out by conventionally known methods such as liquid spraying or ultrasonic spraying, and the droplets sprayed into the flame are instantly dried by the flame, and the organic solvent contained in the droplets is instantly dried by the flame. is combusted, the porous silica obtained by the above-mentioned hydrolysis is made non-porous by the heat of combustion, and easily and efficiently becomes non-porous spherical silica fine particles.
このようにして得られた無孔質の球状シリカ微粒子はこ
の火炎処理によっても火炎温度が５００〜１．３００℃
とされているので融着せず、したがって平均粒径は上記
した加水分解時の平均粒径０．２〜５μｍのままのもの
となる。The nonporous spherical silica fine particles obtained in this way have a flame temperature of 500 to 1.300°C even after this flame treatment.
Therefore, the average particle size remains the same as the above-mentioned average particle size during hydrolysis of 0.2 to 5 μm.
また、多孔質度は細孔のない球状シリカ微粒子の比表面
積ＡＳ ［ｍ２／ｇ］が平均粒径をＤ ［ｒｖ］とする
と式
％式％（１）
で示されるし、Ｄの単位をμｍとすればＡ、 ＝２．７
２／Ｄ ・・・（２）で示され、多孔質の
球状シリカ徹粒子は細孔が形成する表面があるために細
孔のない球状シリカ微粒子よりもその比表面積が大きく
なり、この細孔による表面を含む実測の比表面積Ｓ Ａ
［ｍ２／ｇｌと上記した粒径より計算された理論値で
ある比表面積Ａ３との比が多孔質度Ｐとして表わされる
。In addition, the degree of porosity is expressed by the formula % (1) where the specific surface area AS [m2/g] of spherical silica fine particles without pores is the average particle diameter D [rv], and the unit of D is μm. Then A, =2.7
2/D...(2), porous spherical silica particles have a surface with pores, so their specific surface area is larger than that of spherical silica particles without pores, and these pores Measured specific surface area including the surface S A
[The ratio between m2/gl and the specific surface area A3, which is a theoretical value calculated from the above particle size, is expressed as the degree of porosity P.
Ｐ ＝ Ｓ Ａ／Ａ、 ・・・（３）
したがって、完全な無孔賞球では実測される比表面積は
平坦な外皮表面分のみであるので、粒径基準の理論比表
面積（＾、）と一致し、多孔質度Ｐは１．０となる。一
方、微細な細孔をもつ多孔質床では実測される比表面積
が外皮表面に加え、細孔による表面を含むので、理論比
表面積（八、）より大きくなり、Ｐは１．０以上となる
。上記した加水分解により得られた球状シリカは多くの
細孔をもつものであることから、例えば粒径が０．５μ
ｍのものはその実測比表面積Ｓ＾が約ｓｏｗ”／ｇであ
り、このものの理論比表面積は上記（２）式からＡｓ
＝２．７２１０．５ ＝５．４４となるので、このとき
のＰは５０７５．４４＝ ９．１９となるのである。こ
のようにＰ値が２以上では無孔化が不充分で充填剤とし
て用いた場合、問題が生じる。−力木発明の球状シリカ
微粒子は上記の条件の火炎処理で無孔質化されているの
で実質的に細孔をもたないものとなり、それ故に（３）
式中のＳＡが減少し、Ｐ値も２．０以下のものとなり、
充填剤としてすぐれたものとなる。P=SA/A, ...(3)
Therefore, in a completely non-porous ball, the measured specific surface area is only the flat surface of the outer shell, so it matches the theoretical specific surface area (^,) based on the particle size, and the porosity P is 1.0. . On the other hand, in the case of a porous bed with fine pores, the actually measured specific surface area includes the surface of the pores in addition to the outer skin surface, so it is larger than the theoretical specific surface area (8), and P is 1.0 or more. . Since the spherical silica obtained by the above hydrolysis has many pores, the particle size is, for example, 0.5μ.
The actual specific surface area S^ of the one with m is about sow''/g, and the theoretical specific surface area of this one is given by the above equation (2).
=2.7210.5 =5.44, so P at this time becomes 5075.44=9.19. As described above, when the P value is 2 or more, the non-porous property is insufficient and problems arise when used as a filler. - The spherical silica fine particles of Rikiki's invention are made non-porous by flame treatment under the above conditions, so they have virtually no pores, and therefore (3)
The SA in the formula decreases, the P value also becomes less than 2.0,
It is an excellent filler.
また、ここに得られた球状シリカ微粒子の粒径のバラつ
き（単分散性）は標準偏差σと平均粒径りとの比で示さ
れる変動係数ＣＶで表わされ、ＣＶ−σ／Ｄ
・・・（４）このＣｖはバラつきの少ない程小さく
なるが、本発明の球状シリカ微粒子はアルコキシシラン
の加水分解によって得られた単分散性の良好な状態のも
のがそのまま火炎処理によって乾燥、無孔化され、この
ものは融着することもないのでこの変動係数ＣＶは０．
１５以下と非常に小さいものになる。In addition, the variation in particle size (monodispersity) of the obtained spherical silica fine particles is expressed by the coefficient of variation CV, which is the ratio of the standard deviation σ to the average particle size, and CV-σ/D
(4) This Cv becomes smaller as the variation decreases, but the spherical silica fine particles of the present invention are obtained by hydrolyzing alkoxysilane and are in a good state of monodispersity. The coefficient of variation CV is 0.
It is very small, less than 15.
［実施例］
つぎに本発明の実施例および比較例をあげるが、例示し
た写真は走査型電子顕微ｆｉＴ−２０［日本電子■製］
を用いて撮影した電子顕微鏡写真であり、この球状シリ
カ微粒子の平均粒径、標準偏差はこの電子顕微鏡から測
定したもの、また比表面積はマイクロメテリックス・フ
ローソーブｎ −２３００形［島原製作所■製］を用い
て測定したものである。[Example] Next, Examples and Comparative Examples of the present invention will be given. The illustrated photographs are taken using a scanning electron microscope fiT-20 [manufactured by JEOL Ltd.]
This is an electron micrograph taken using an electron microscope.The average particle size and standard deviation of the spherical silica particles are those measured using this electron microscope, and the specific surface area is Micrometelix Flowsorb N-2300 type [manufactured by Shimabara Seisakusho ■] It was measured using
実施例１
温度計およびプロペラ型攪拌翼を設けた５１のフラスコ
に、２．９％アンモニア水８８０ｍ！ 、水４１０ｍＡ
’ 、メタノール２ 、０８６ｍ１！を仕込んで内温を
２０℃に保ち、フラスコ内を６００ｒｐｍで攪拌しなが
らここにテトラメトキシシラン６８．４ｍｊとメタノー
ル４４０ｍｊどの混合溶液を７５分かけて滴下し、滴下
終了後も１５分間攪拌を行なったところ、白色のスラリ
ーが得られ、このスラリーにはシリカ分７．０％、水２
０．９％、メタノール６７．０％、アンモニア５．１％
が含まれていた。Example 1 880 m of 2.9% ammonia water was placed in a 51 flask equipped with a thermometer and a propeller type stirring blade! , water 410mA
', methanol 2, 086ml! While stirring the inside of the flask at 600 rpm, a mixed solution of 68.4 mj of tetramethoxysilane and 440 mj of methanol was added dropwise over 75 minutes, and stirring was continued for 15 minutes after the addition was completed. As a result, a white slurry was obtained, and this slurry contained 7.0% silica and 22% water.
0.9%, methanol 67.0%, ammonia 5.1%
was included.
ついで、このスラリーを酸素ガスと共に火炎温度を１，
１８０℃に調整した酸水素火炎中に噴霧し、生成した微
粒子をバッグフィルターで捕集したところ、白色のシリ
カ粉末が得られた。Next, this slurry was heated with oxygen gas to a flame temperature of 1.
When it was sprayed into an oxyhydrogen flame adjusted to 180°C and the generated fine particles were collected with a bag filter, white silica powder was obtained.
なお、この火炎温度はバーナーに供給する水素量および
発生する燃焼熱を顕然として奪うためバーナーに供給す
るイナートとしてのＮ２ガス量により調整した。Note that this flame temperature was adjusted by the amount of hydrogen supplied to the burner and the amount of N2 gas as inert supplied to the burner in order to clearly take away the generated combustion heat.
つぎにこのシリカ粉末を電子顕微鏡で撮影したところ、
第１図に示したものが得られ、これよりその平均粒径、
標準偏差をしらべたところ、この平均粒径は０．６４μ
ｍ％標準偏差は０．０７８μｍであり、変動係数は０．
１２２ 、またＢＥＴ表面積は４．５ｍ２７ｇでその多
孔質度は１．０６であった。Next, when we photographed this silica powder using an electron microscope, we found that
The particles shown in Figure 1 were obtained, and from this, the average particle size,
When we looked at the standard deviation, the average particle size was 0.64μ.
The m% standard deviation is 0.078 μm, and the coefficient of variation is 0.
122, and the BET surface area was 4.5 m27 g, and its porosity was 1.06.
実施例２．比較例１〜２
実施例１で得られたスラリーを酸素ガスと共に火炎温度
を８０４℃（実施例２ ） 、 １，３８０℃（比較例
１ ） 、４５０℃（比較例２）に調整した酸水素火炎
中に噴霧して乾燥、無孔化処理し、生成した微粒子をバ
ッグフィルターで捕集したところ、実施例２．比較例１
では白色粉末が得られたが、比較例２では薄茶色に着色
した粉末が得られた。Example 2. Comparative Examples 1 to 2 Oxyhydrogen prepared by adding oxygen gas to the slurry obtained in Example 1 and adjusting the flame temperature to 804°C (Example 2), 1,380°C (Comparative Example 1), or 450°C (Comparative Example 2) Example 2 was sprayed into a flame, dried and treated to make it non-porous, and the generated fine particles were collected with a bag filter. Comparative example 1
In Comparative Example 2, a white powder was obtained, but in Comparative Example 2, a light brown colored powder was obtained.
つぎにこれらの粉末の電子顕微鏡写真を撮影したところ
、実施例のものは第２図、比較例１のものは第３図、比
較例２のものは第゛４図に示したとおりのものとなり、
これから測定したこれらの粉末の平均粒径、標準偏差、
および変動係数、ならびに比表面積、多孔質度について
は第１表に示したとおりの結果が得られ、これより比較
例１ではシリカの融着があり、比較例２では無孔化の完
了していないことが確認された。Next, electron micrographs of these powders were taken, and the results were as shown in Figure 2 for Example, Figure 3 for Comparative Example 1, and Figure 4 for Comparative Example 2. ,
The average particle size, standard deviation, and
The results shown in Table 1 were obtained for the coefficient of variation, specific surface area, and porosity, and it can be seen that in Comparative Example 1, there was fusion of silica, and in Comparative Example 2, no porosity was completed. It was confirmed that there was no such thing.
第 １ 表
［発明の効果］
本発明は前記したように、多孔質度が１．０〜２．０で
あり、平均粒径が０．２〜５．０μｍで、平均粒径の変
動係数が０．１５である球状シリカ微粒子およびアルコ
キシシランの加水分解で得たシリカを５００〜１，３０
０℃の火炎中で乾燥、無孔化した上記した球状シリカ微
粒子の製造方法に関するものであるが、この球状シリカ
微粒子は実質的に無孔質化されているのでプラスチック
パッケージ用充填剤として有用とされるものであり、こ
の製造方法によれば目的とする球状シリカ微粒子を容易
にかつ効率的に得ることができるという有利性が与えら
れる。Table 1 [Effects of the Invention] As described above, the present invention has a porosity of 1.0 to 2.0, an average particle size of 0.2 to 5.0 μm, and a coefficient of variation of the average particle size. Spherical silica fine particles with a particle size of 0.15 and silica obtained by hydrolysis of alkoxysilane have a particle size of 500 to 1,30
The present invention relates to a method for producing the above-mentioned spherical silica fine particles which are dried in a flame at 0°C and made non-porous.Since the spherical silica fine particles are substantially non-porous, they are useful as fillers for plastic packages. This production method has the advantage that the desired spherical silica fine particles can be obtained easily and efficiently.
第１図は本発明の実施例１で得られた球状シリカ微粒子
の構造を示す電子顕微鏡写真、第２図は本発明の実施例
２で得られた球状シリカ微粒子の構造を示す電子顕微鏡
写真、第３図は比較例１で得られた球状シリカ微粒子の
構造を示す電子顕微鏡写真、第４図は比較例２で得られ
た球状シリカ微粒子の構造を示す電子顕微鏡写真である
。
図FIG. 1 is an electron micrograph showing the structure of spherical silica fine particles obtained in Example 1 of the present invention, FIG. 2 is an electron micrograph showing the structure of spherical silica fine particles obtained in Example 2 of the present invention, FIG. 3 is an electron micrograph showing the structure of the spherical silica fine particles obtained in Comparative Example 1, and FIG. 4 is an electron micrograph showing the structure of the spherical silica fine particles obtained in Comparative Example 2. figure
Claims (1)
２〜５．０μｍで、平均粒径の変動係数が０．１５以下
であることを特徴とする球状シリカ微粒子。 ２、アルコキシシランを加水分解して得た微細球状シリ
カを含む溶液を火炎温度が５００〜１，３００℃の火炎
中で乾燥、無孔化してなることを特徴とする請求項１に
記載の球状シリカ微粒子の製造方法。[Claims] 1. The porosity is 1.0 to 2.0, and the average particle size is 0.
Spherical silica fine particles having a mean particle diameter of 2 to 5.0 μm and a coefficient of variation of 0.15 or less. 2. The spherical shape according to claim 1, which is obtained by drying a solution containing fine spherical silica obtained by hydrolyzing an alkoxysilane in a flame at a flame temperature of 500 to 1,300°C to make it non-porous. Method for producing silica fine particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11909289A JPH02296711A (en) | 1989-05-12 | 1989-05-12 | Spherical silica particle and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11909289A JPH02296711A (en) | 1989-05-12 | 1989-05-12 | Spherical silica particle and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02296711A true JPH02296711A (en) | 1990-12-07 |
| JPH0470257B2 JPH0470257B2 (en) | 1992-11-10 |
Family
ID=14752702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11909289A Granted JPH02296711A (en) | 1989-05-12 | 1989-05-12 | Spherical silica particle and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02296711A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0786505A2 (en) * | 1996-01-25 | 1997-07-30 | W.L. GORE & ASSOCIATES, INC. | Adhesive-filler film composite and method of making |
| WO2000068300A1 (en) * | 1999-05-06 | 2000-11-16 | Merck Patent Gmbh | Method for producing bead polymers |
| WO2006030782A1 (en) * | 2004-09-14 | 2006-03-23 | Japan Science And Technology Agency | Ceramic particle group and method for production thereof and use thereof |
| US7070748B2 (en) | 2000-09-27 | 2006-07-04 | Mitsubishi Rayon Co., Ltd. | Non-porous spherical silica and method for production thereof |
| JP2012504094A (en) * | 2008-09-30 | 2012-02-16 | サン−ゴベン・セントル・ドゥ・レシェルシェ・エ・デチュード・ユーロペアン | Zirconium oxide powder |
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|---|---|---|---|---|
| JPS6272514A (en) * | 1985-09-25 | 1987-04-03 | メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Spherical sio2 particle |
| JPS63310714A (en) * | 1988-06-07 | 1988-12-19 | Tokuyama Soda Co Ltd | Silica particles |
| JPH01145317A (en) * | 1987-12-01 | 1989-06-07 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of spherical fine particle of silica |
| JPH02288A (en) * | 1987-12-18 | 1990-01-05 | Beecham Group Plc | Substituted penem derivative |
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1989
- 1989-05-12 JP JP11909289A patent/JPH02296711A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6272514A (en) * | 1985-09-25 | 1987-04-03 | メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Spherical sio2 particle |
| JPH01145317A (en) * | 1987-12-01 | 1989-06-07 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of spherical fine particle of silica |
| JPH02288A (en) * | 1987-12-18 | 1990-01-05 | Beecham Group Plc | Substituted penem derivative |
| JPS63310714A (en) * | 1988-06-07 | 1988-12-19 | Tokuyama Soda Co Ltd | Silica particles |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0786505A2 (en) * | 1996-01-25 | 1997-07-30 | W.L. GORE & ASSOCIATES, INC. | Adhesive-filler film composite and method of making |
| EP0786505A3 (en) * | 1996-01-25 | 1998-10-21 | W.L. GORE & ASSOCIATES, INC. | Adhesive-filler film composite and method of making |
| WO2000068300A1 (en) * | 1999-05-06 | 2000-11-16 | Merck Patent Gmbh | Method for producing bead polymers |
| US6492471B1 (en) | 1999-05-06 | 2002-12-10 | Merck Patent Gesellschaft Mit Beschraenkter Haftung | Method for producing bead polymers |
| US7070748B2 (en) | 2000-09-27 | 2006-07-04 | Mitsubishi Rayon Co., Ltd. | Non-porous spherical silica and method for production thereof |
| WO2006030782A1 (en) * | 2004-09-14 | 2006-03-23 | Japan Science And Technology Agency | Ceramic particle group and method for production thereof and use thereof |
| JPWO2006030782A1 (en) * | 2004-09-14 | 2008-05-15 | 独立行政法人科学技術振興機構 | Ceramic particle group, method for producing the same and use thereof |
| KR100898218B1 (en) * | 2004-09-14 | 2009-05-18 | 재팬 사이언스 앤드 테크놀로지 에이젼시 | Ceramic Particle Group and Method for Production Thereof and Use Thereof |
| US7749429B2 (en) | 2004-09-14 | 2010-07-06 | Japan Science And Technology Agency | Ceramic particle group and method for production thereof and use thereof |
| US8153255B2 (en) | 2004-09-14 | 2012-04-10 | Japan Science And Technology Agency | Ceramic particle group comprising sintered particles of hydroxyapatite |
| JP2012504094A (en) * | 2008-09-30 | 2012-02-16 | サン−ゴベン・セントル・ドゥ・レシェルシェ・エ・デチュード・ユーロペアン | Zirconium oxide powder |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0470257B2 (en) | 1992-11-10 |
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