JP5017650B2 - Method for preparing hollow silica particles - Google Patents
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- JP5017650B2 JP5017650B2 JP2007059504A JP2007059504A JP5017650B2 JP 5017650 B2 JP5017650 B2 JP 5017650B2 JP 2007059504 A JP2007059504 A JP 2007059504A JP 2007059504 A JP2007059504 A JP 2007059504A JP 5017650 B2 JP5017650 B2 JP 5017650B2
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Description
本発明は炭酸カルシウムを芯物質として珪酸テトラエチルに代表されるシリコンアルコキシドの加水分解により殻を形成後、酸により芯を溶解させる一連のプロセスからなるシリカ中空粒子製造方法に関するものである。 The present invention relates to a method for producing silica hollow particles comprising a series of processes in which a shell is formed by hydrolysis of silicon alkoxide represented by tetraethyl silicate using calcium carbonate as a core substance, and then the core is dissolved by an acid.
一般にシリカに代表される無機物質から構成される中空粒子は噴霧熱分解法のような発泡により中空構造を得る方法と、芯(コア)となる物質に殻の原料を析出させたのちに芯を除去する方法(テンプレート法)によって製造される。 In general, hollow particles composed of an inorganic substance typified by silica are obtained by foaming, such as spray pyrolysis, and the core is formed after depositing the shell material on the core material. Manufactured by a removal method (template method).
テンプレート法では形状の均一な中空粒子が得られる。代表的なテンプレートとしてはラテックス粒子、エマルションなどが挙げられる。しかしこれらを用いた場合はテンプレート粒子の特性として球状の中空粒子が得られる。 By the template method, hollow particles having a uniform shape can be obtained. Typical templates include latex particles and emulsions. However, when these are used, spherical hollow particles can be obtained as template particle characteristics.
特許文献1にあるように、炭酸カルシウムに代表される無機粒子をテンプレートとした場合、その結晶形状を反映した様々な形状の粒子を得る事が出来る。また、コアは塩酸などの酸で容易に除去される。 As described in Patent Document 1, when inorganic particles typified by calcium carbonate are used as templates, particles having various shapes reflecting the crystal shape can be obtained. The core is easily removed with an acid such as hydrochloric acid.
しかし上記の特許文献の通り炭酸カルシウムコアの周りにシリカ殻を形成させるプロセスにおけるシリコンアルコキシドの加水分解では触媒として通常アンモニア水が用いられる。
従来法では触媒にアンモニア水を用いるため毒性、臭気などの問題があった。またそれらの問題のために排気設備が必要であった。 The conventional method has problems such as toxicity and odor because ammonia water is used as a catalyst. Moreover, exhaust equipment was necessary for those problems.
本発明は、上記従来の実情に鑑みてなされたものであって、臭気及び毒性のない反応プロセスの開発を課題としている。 This invention is made | formed in view of the said conventional situation, Comprising: Development of the reaction process without an odor and toxicity is made into the subject.
上記の問題を解決するためにアンモニア水溶液の替わりに炭酸ナトリウム水溶液を触媒として用いることを特徴とする。 In order to solve the above problem, an aqueous sodium carbonate solution is used as a catalyst instead of the aqueous ammonia solution.
炭酸カルシウムを分散させたアルコール溶液に炭酸ナトリウム水溶液、シリコンアルコキシドを順次添加する。攪拌または振とうさせシリコンアルコキシドの加水分解反応を進行させた後にフィルターによるろ過あるいは遠心分離により未反応のシリコンアルコキシドおよび炭酸ナトリウムを除去する。 A sodium carbonate aqueous solution and a silicon alkoxide are sequentially added to an alcohol solution in which calcium carbonate is dispersed. After the silicon alkoxide is hydrolyzed by stirring or shaking, unreacted silicon alkoxide and sodium carbonate are removed by filtration through a filter or centrifugation.
続いて、酸を添加してコアの炭酸カルシウムを溶解させ、ろ過あるいは遠心分離によってシリカ粒子を分離する。このとき分散性を保つために必要に応じて界面活性剤などの添加、pHの調整などを行う。 Subsequently, an acid is added to dissolve the calcium carbonate in the core, and the silica particles are separated by filtration or centrifugation. At this time, in order to maintain dispersibility, addition of a surfactant or the like, adjustment of pH, etc. are performed as necessary.
アンモニア水溶液と比較して、炭酸ナトリウム水溶液は室温で安定であり、無臭である。蒸発する気体も二酸化炭素であり合成で発生する量ではアンモニアよりも人体に対して無害である。 Compared with aqueous ammonia solution, aqueous sodium carbonate solution is stable at room temperature and odorless. The gas that evaporates is also carbon dioxide, and the amount generated in the synthesis is harmless to the human body than ammonia.
炭酸ナトリウム水溶液は、安定な粉末から容易に新鮮な水溶液が調製されるためアンモニア水ほど保管に注意を払う必要がない。反応に用いられた炭酸ナトリウムは反応直後のろ過および、塩酸によるコア溶解後のろ過によって容易に除去される。 The aqueous sodium carbonate solution is easily prepared from a stable powder, so that it is not necessary to pay as much attention to storage as aqueous ammonia. Sodium carbonate used in the reaction is easily removed by filtration immediately after the reaction and filtration after dissolving the core with hydrochloric acid.
一次粒子径約80nmの略立方体状の炭酸カルシウム粒子水分散液(8.9重量%)3.2gを15mlのエチルアルコールにより希釈し超音波照射によってよく分散させた。 3.2 g of a substantially cubic calcium carbonate particle aqueous dispersion (8.9 wt%) having a primary particle diameter of about 80 nm was diluted with 15 ml of ethyl alcohol and well dispersed by ultrasonic irradiation.
つづいて炭酸ナトリウム1.0moldm−3水溶液を1ml加え、さらにテトラ珪酸エチルを1ml添加し、20℃恒温水槽中で1時間振とうさせた。 Subsequently, 1 ml of an aqueous solution of sodium carbonate 1.0 moldm −3 was added, and further 1 ml of ethyl tetrasilicate was added, followed by shaking in a constant temperature water bath at 20 ° C. for 1 hour.
反応終了後、両親媒性フィルター(孔径0.1mm)を用い減圧ろ過を行った。続いて3N塩酸を1ml加えてコアの炭酸カルシウム粒子除去を行った。 After completion of the reaction, vacuum filtration was performed using an amphiphilic filter (pore diameter: 0.1 mm). Subsequently, 1 ml of 3N hydrochloric acid was added to remove the core calcium carbonate particles.
粒子の透過電子顕微鏡像を図1に示す。均一な10nm程度のシリカ殻より構成される中空粒子が確認できる。 A transmission electron microscope image of the particles is shown in FIG. Hollow particles composed of a uniform silica shell of about 10 nm can be confirmed.
断熱塗料、低誘電材料、軽量フィラー、反射防止膜などに適用可能である。 It can be applied to heat insulating paints, low dielectric materials, lightweight fillers, antireflection films and the like.
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JP2007059504A JP5017650B2 (en) | 2007-03-09 | 2007-03-09 | Method for preparing hollow silica particles |
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Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP5223411B2 (en) * | 2008-03-27 | 2013-06-26 | Jsr株式会社 | Method for producing silica-based hollow particles |
JP5810362B2 (en) * | 2011-03-09 | 2015-11-11 | 国立大学法人 名古屋工業大学 | Method for producing nano hollow particles comprising silica shell |
KR102038494B1 (en) * | 2017-07-25 | 2019-10-30 | 울산과학기술원 | Silicon sheet, manufacturing method thereof, and lithium secondary battery including the same |
KR102221607B1 (en) * | 2019-08-05 | 2021-03-02 | 울산과학기술원 | Silicon sheet, manufacturing method thereof, and lithium secondary battery including the same |
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JPH0967296A (en) * | 1995-06-22 | 1997-03-11 | Daicel Chem Ind Ltd | Production of carboxylic acid |
JP3999827B2 (en) * | 1996-01-31 | 2007-10-31 | 東レ・ダウコーニング株式会社 | Method for producing organopentasiloxane |
JP3859277B2 (en) * | 1996-08-28 | 2006-12-20 | ライオン株式会社 | Method for producing oligoglycerol and solid catalyst |
JP2003300926A (en) * | 2002-04-08 | 2003-10-21 | Nippon Shokubai Co Ltd | METHOD FOR PRODUCING alpha-HYDROXYCARBOXYLIC ACID OR alpha- OXOCARBOXYLIC ACID |
JP4654428B2 (en) * | 2004-03-18 | 2011-03-23 | 国立大学法人 名古屋工業大学 | Highly dispersed silica nano hollow particles and method for producing the same |
JP4861634B2 (en) * | 2005-03-18 | 2012-01-25 | 国立大学法人 名古屋工業大学 | Method for producing silica hollow particles |
JP2007056158A (en) * | 2005-08-25 | 2007-03-08 | Nagoya Institute Of Technology | Resin composition and wiring circuit board using the same |
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