JP2004142999A - Method for producing spherical zinc oxide - Google Patents
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- JP2004142999A JP2004142999A JP2002310617A JP2002310617A JP2004142999A JP 2004142999 A JP2004142999 A JP 2004142999A JP 2002310617 A JP2002310617 A JP 2002310617A JP 2002310617 A JP2002310617 A JP 2002310617A JP 2004142999 A JP2004142999 A JP 2004142999A
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、粒子形状が球状の酸化亜鉛の製造方法に関するものである。
【０００２】
【従来の技術】
従来、酸化亜鉛粉末は、顔料、医薬品、触媒あるいは電子材料等の分野で使用されており、その形状としては、鱗片状、球状、針状等の各種形状を有する酸化亜鉛が開発されている。
このうち、形状が球状である酸化亜鉛は、特に紫外線防御機能の面で優れていることから、塗料や化粧品等の分野においてその活用が期待されている。
【０００３】
球状酸化亜鉛の合成方法としては、例えば、ミスト焼成法と呼ばれる方法が知られている。しかし、この方法では中空体ができやすく、また真球状の生成物を得ることが困難であった。
【０００４】
特開昭６３−２８８９１４号では、低温希薄亜鉛蒸気を酸素と接触させることによって、球状酸化亜鉛を製造する方法が提案されている。
しかしながら、この方法では、高温（５５０℃〜８００℃）の亜鉛溶湯に不活性ガスを吹き込むことによって亜鉛蒸気を発生させる必要がある。また、亜鉛蒸気には、毒性があるという問題点もある。
【０００５】
また、特開平１１−４９５１６号では、有機亜鉛化合物を用いた球状酸化亜鉛の合成方法が開示されている。
しかしながら、この方法では焼成時の温度を高く（６００℃〜８００℃）設定する必要がある。また、出発原料に有機亜鉛化合物を使用しているため、焼成過程に有毒ガスが発生するおそれがある。さらに、得られる酸化亜鉛の収率が低く、しかも他の形状の酸化亜鉛との混在下でしか得ることができない。
【０００６】
【特許文献１】特開昭６３−２８８９１４号公報（特許請求の範囲）
【特許文献２】特開平１１−４９５１６号公報（特許請求の範囲）
【０００７】
【発明が解決しようとする課題】
本発明は、このような点に鑑みなされたものである。
本発明では、有毒ガス等が発生するおそれがなく、比較的低い温度で合成可能な球状酸化亜鉛の製造方法を提供することを目的とする。
【０００８】
【課題を解決するための手段】
上記課題を解決するため、本発明者は鋭意検討の結果、炭酸イオン及び／または炭酸水素イオン、アンモニウムイオンを含む水溶液（Ｉ）と、亜鉛イオンを含む水溶液（ＩＩ）とを混合して、得られた生成物を３００℃以上で焼成する酸化亜鉛の製造方法において、水溶液のイオン濃度とｐＨを制御することによって球状の酸化亜鉛が得られることを見出し、本発明を完成させるに至った。
【０００９】
すなわち、本発明は以下の特徴を有するものである。
１．炭酸イオン及び／または炭酸水素イオン、アンモニウムイオンを含む水溶液（Ｉ）と、亜鉛イオンを含む水溶液（ＩＩ）とを混合して、得られた生成物を３００℃以上で焼成する酸化亜鉛の製造方法であって、
水溶液（Ｉ）における炭酸イオンと炭酸水素イオンの合計イオン濃度よりも、水溶液（ＩＩ）における亜鉛イオン濃度を低く設定し、かつ、水溶液（ＩＩ）のｐＨを２未満とすることを特徴とする球状酸化亜鉛の製造方法。
２．水溶液（Ｉ）の温度を１５〜４５℃とすることを特徴とする１．記載の球状酸化亜鉛の製造方法。
【００１０】
【発明の実施の形態】
以下、本発明をその実施の形態とともに詳細に説明する。
【００１１】
本発明では、まず、炭酸イオン及び／または炭酸水素イオン、アンモニウムイオンを含む水溶液（Ｉ）と、亜鉛イオンを含む水溶液（ＩＩ）とを混合する。
【００１２】
水溶液（Ｉ）は、炭酸イオン及び／または炭酸水素イオンと、アンモニウムイオンとを含むものである。これらイオンの発生源は特に限定されないが、炭酸水素アンモニウム、炭酸アンモニウムから選ばれる１種以上が好適である。
水溶液（ＩＩ）における亜鉛イオンの発生源としては、例えば、塩化亜鉛、硫酸亜鉛、硝酸亜鉛、酢酸亜鉛等が挙げられる。このうち、本発明では塩化亜鉛が好適である。
【００１３】
本発明では、水溶液（Ｉ）に水溶液（ＩＩ）を徐々に滴下することによって、水酸化イオンと炭酸イオンと亜鉛イオンとからなる物質（以下「球状生成物」という）が生成する。このような球状生成物は、微細な核物質が形成した後、球状に粒子成長したものであると考えられる。
【００１４】
水溶液（Ｉ）に水溶液（ＩＩ）を滴下する際には、水溶液（Ｉ）における炭酸イオンと炭酸水素イオンの合計イオン濃度（以下単に「水溶液（Ｉ）の濃度」という）よりも、水溶液（ＩＩ）における亜鉛イオン濃度（以下単に「水溶液（ＩＩ）の濃度」という）を低く設定し、さらに、水溶液（ＩＩ）のｐＨを２未満に設定する。このような条件下であれば、球状生成物を得ることができる。
【００１５】
水溶液（ＩＩ）の濃度が、水溶液（Ｉ）の濃度以上である場合は、急激な中和反応が生じてしまうため、球状の生成物を得ることができない。本発明では、水溶液（ＩＩ）の濃度が水溶液（Ｉ）の濃度よりも低いことが必須条件であるが、好適な濃度条件は、水溶液（Ｉ）の濃度に対する水溶液（ＩＩ）の濃度を３０％以下、好ましくは１５％以下とすることである。このような濃度条件にすれば、球状生成物の収率をより高めることができる。
水溶液（ＩＩ）のｐＨが２以上である場合は、球状生成物を得ることができない。水溶液（ＩＩ）のより好適なｐＨ範囲は１以下である。
【００１６】
本発明では、水溶液（Ｉ）の温度を１５〜４５℃（さらには２０〜４５℃）に設定することが望ましい。水溶液（Ｉ）の温度がこのような範囲内であれば、より確実に球状生成物を得ることができる。
水溶液（ＩＩ）の温度は、水溶液（Ｉ）の温度より低く設定しておくことが望ましい。
【００１７】
水溶液（Ｉ）に対する水溶液（ＩＩ）の混合量は、特に限定されないが、炭酸イオンと炭酸水素イオンの総モル数より、亜鉛イオンの総モル数が小さくなるようにすることが望ましい。
【００１８】
水溶液（Ｉ）と水溶液（ＩＩ）との混合によって生成した球状生成物を３００℃以上の温度で焼成すれば、脱水、脱炭酸が生じ、球状酸化亜鉛を得ることができる。焼成温度は３００℃以上であればよいが、好ましくは３００℃〜６００℃、より好ましくは３５０〜５００℃である。
焼成工程については、特別な雰囲気を必要とせず、通常の焼成装置を使用して大気中、開放系で行えばよい。場合によっては、焼成段階を非酸化性雰囲気に調整することもできる。
【００１９】
以上の方法によって得られる酸化亜鉛は、球状の形状を有するものである。その粒子径は、例えば水溶液（ＩＩ）滴下時における水溶液（Ｉ）の攪拌速度等を適宜設定することによって調整することができる。球状粒子の粒子径は、通常０．０１〜１０μｍ程度である。
【００２０】
本発明の球状酸化亜鉛は、例えば、紫外線吸収剤、導電性材料、触媒担体、補強剤、充填剤、顔料、加硫促進助剤等として用いることができる。利用分野としては、塗料、インキ、絵具、ガラス、釉、メッキ、撥水剤、歯科セメント、ガスセンサー、医薬品、石油精製、電池、電子写真材料、蛍光体、電磁波吸収材、吸音材等が挙げられる。
特に、本発明酸化亜鉛は球状になることで紫外線防御性能が高くなるため、利用される用途によっては顕著な性能向上が予測される。例えば、本発明酸化亜鉛を樹脂等と複合して紫外線防御材に用いた場合は、球状酸化亜鉛自体の紫外線防御性能が高いため、フレーク状の酸化亜鉛等に比べ少量で十分な紫外線防御性能が期待できる。
なお、本発明酸化亜鉛を上述のような各種用途に使用する場合には、球状形状を損なわない程度に様々な処理を施すこともできる。
【００２１】
【実施例】
以下に実施例を示し、本発明をより詳細に説明する。
【００２２】
（実施例１）
１．５ｍｏｌ／ｌの炭酸水素アンモニウム水溶液４００ｍｌに対し、０．２ｍｏｌ／ｌ、ｐＨ１の塩化亜鉛水溶液２００ｍｌを徐々に滴下した。なお、炭酸水素アンモニウム水溶液の温度は２０℃とした。
このようにして得られた生成物を洗浄、ろ過し、さらに４００℃で焼成した。得られた酸化亜鉛の形状を、走査型電子顕微鏡（日本電子製：ＪＳＭ５３０１ＬＶ）を用いて観察したところ、真球に近い球状粒子であることが認められた（図１）。
【００２３】
（実施例２）
１．５ｍｏｌ／ｌの炭酸水素アンモニウム水溶液４００ｍｌに対し、０．２ｍｏｌ／ｌ、ｐＨ１の塩化亜鉛水溶液２００ｍｌを徐々に滴下した。なお、炭酸水素アンモニウム水溶液の温度は４０℃とした。
このようにして得られた生成物を洗浄、ろ過し、さらに４００℃で焼成した。得られた酸化亜鉛の形状は、真球に近い球状粒子であることが認められた（図２）。
【００２４】
（実施例３）
１．５ｍｏｌ／ｌの炭酸アンモニウム水溶液４００ｍｌに対し、０．２ｍｏｌ／ｌ、ｐＨ１の塩化亜鉛水溶液２００ｍｌを徐々に滴下した。なお、炭酸アンモニウム水溶液の温度は２０℃とした。
このようにして得られた生成物を洗浄、ろ過し、さらに４００℃で焼成した。得られた酸化亜鉛の形状は、真球に近い球状粒子であることが認められた（図３）。
【００２５】
（比較例１）
１．５ｍｏｌ／ｌの炭酸水素アンモニウム水溶液４００ｍｌに対し、０．２ｍｏｌ／ｌ、ｐＨ３の塩化亜鉛水溶液２００ｍｌを徐々に滴下した。なお、炭酸水素アンモニウム水溶液の温度は４０℃とした。
このようにして得られた生成物を洗浄、ろ過し、さらに４００℃で焼成した。得られた酸化亜鉛の形状はウニ状となり、球状酸化亜鉛を得ることはできなかった。
【００２６】
（比較例２）
１．５ｍｏｌ／ｌのアンモニウム水溶液４００ｍｌに対し、０．２ｍｏｌ／ｌ、ｐＨ３の塩化亜鉛水溶液２００ｍｌを徐々に滴下したところ、球状生成物を得ることができなかった。
【００２７】
【発明の効果】
本発明によれば、真球に近い球状酸化亜鉛を得ることができる。
その製造工程においては合成温度、焼成温度が低く、他の形状の酸化亜鉛がほとんど混在せずに、球状形状の酸化亜鉛を効率的に合成することができる。
【図面の簡単な説明】
【図１】実施例１で合成された球状酸化亜鉛の電子顕微鏡写真である。
【図２】実施例２で合成された球状酸化亜鉛の電子顕微鏡写真である。
【図３】実施例３で合成された球状酸化亜鉛の電子顕微鏡写真である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing zinc oxide having a spherical particle shape.
[0002]
[Prior art]
Conventionally, zinc oxide powder has been used in the fields of pigments, pharmaceuticals, catalysts, electronic materials, and the like, and as its shape, zinc oxide having various shapes such as flakes, spheres, and needles has been developed.
Among them, zinc oxide having a spherical shape is expected to be used in the fields of paints, cosmetics, and the like, because zinc oxide is particularly excellent in terms of an ultraviolet protection function.
[0003]
As a method for synthesizing spherical zinc oxide, for example, a method called a mist firing method is known. However, in this method, a hollow body is easily formed, and it is difficult to obtain a spherical product.
[0004]
JP-A-63-288914 proposes a method for producing spherical zinc oxide by bringing low-temperature diluted zinc vapor into contact with oxygen.
However, in this method, it is necessary to generate zinc vapor by blowing an inert gas into a high-temperature (550 ° C. to 800 ° C.) molten zinc. In addition, there is a problem that zinc vapor is toxic.
[0005]
Japanese Patent Application Laid-Open No. H11-49516 discloses a method for synthesizing spherical zinc oxide using an organic zinc compound.
However, in this method, it is necessary to set a high firing temperature (600 ° C. to 800 ° C.). Further, since an organic zinc compound is used as a starting material, toxic gas may be generated during the firing process. Furthermore, the yield of zinc oxide obtained is low, and it can be obtained only in the presence of other forms of zinc oxide.
[0006]
[Patent Document 1] JP-A-63-288914 (Claims)
[Patent Document 2] JP-A-11-49516 (Claims)
[0007]
[Problems to be solved by the invention]
The present invention has been made in view of such a point.
An object of the present invention is to provide a method for producing spherical zinc oxide that can be synthesized at a relatively low temperature without the risk of generating toxic gas or the like.
[0008]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have made intensive studies and as a result obtained by mixing an aqueous solution (I) containing carbonate ions and / or hydrogen carbonate ions and ammonium ions with an aqueous solution (II) containing zinc ions. In a method for producing zinc oxide in which the obtained product is calcined at 300 ° C. or higher, it has been found that spherical zinc oxide can be obtained by controlling the ion concentration and pH of the aqueous solution, and the present invention has been completed.
[0009]
That is, the present invention has the following features.
1. A method for producing zinc oxide, comprising mixing an aqueous solution (I) containing carbonate ions and / or bicarbonate ions and ammonium ions with an aqueous solution (II) containing zinc ions and calcining the obtained product at 300 ° C. or higher. And
A spherical shape wherein the zinc ion concentration in the aqueous solution (II) is set lower than the total ion concentration of carbonate ion and hydrogen carbonate ion in the aqueous solution (I), and the pH of the aqueous solution (II) is less than 2. A method for producing zinc oxide.
2. The temperature of the aqueous solution (I) is 15 to 45 ° C. A method for producing the spherical zinc oxide according to the above.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail along with its embodiments.
[0011]
In the present invention, first, an aqueous solution (I) containing carbonate ions and / or hydrogen carbonate ions and ammonium ions and an aqueous solution (II) containing zinc ions are mixed.
[0012]
The aqueous solution (I) contains carbonate ions and / or hydrogen carbonate ions and ammonium ions. The source of these ions is not particularly limited, but one or more selected from ammonium bicarbonate and ammonium carbonate is preferred.
Examples of the source of zinc ions in the aqueous solution (II) include zinc chloride, zinc sulfate, zinc nitrate, and zinc acetate. Of these, zinc chloride is preferred in the present invention.
[0013]
In the present invention, by gradually dropping the aqueous solution (II) into the aqueous solution (I), a substance composed of hydroxide ions, carbonate ions, and zinc ions (hereinafter, referred to as “spherical product”) is generated. It is considered that such a spherical product is formed by spherical particle growth after the formation of fine core material.
[0014]
When the aqueous solution (II) is dropped into the aqueous solution (I), the aqueous solution (II) is more concentrated than the total ion concentration of carbonate ions and hydrogen carbonate ions in the aqueous solution (I) (hereinafter simply referred to as “the concentration of the aqueous solution (I)”). ), The zinc ion concentration (hereinafter simply referred to as “the concentration of the aqueous solution (II)”) is set low, and the pH of the aqueous solution (II) is set to less than 2. Under such conditions, a spherical product can be obtained.
[0015]
When the concentration of the aqueous solution (II) is equal to or higher than the concentration of the aqueous solution (I), a sharp neutralization reaction occurs, so that a spherical product cannot be obtained. In the present invention, it is an essential condition that the concentration of the aqueous solution (II) is lower than the concentration of the aqueous solution (I). A preferable concentration condition is that the concentration of the aqueous solution (II) is 30% of the concentration of the aqueous solution (I). Or less, preferably 15% or less. With such a concentration condition, the yield of the spherical product can be further increased.
When the pH of the aqueous solution (II) is 2 or more, a spherical product cannot be obtained. The more preferable pH range of the aqueous solution (II) is 1 or less.
[0016]
In the present invention, it is desirable to set the temperature of the aqueous solution (I) to 15 to 45 ° C (more preferably, 20 to 45 ° C). When the temperature of the aqueous solution (I) is within such a range, a spherical product can be obtained more reliably.
It is desirable that the temperature of the aqueous solution (II) is set lower than the temperature of the aqueous solution (I).
[0017]
The mixing amount of the aqueous solution (II) with respect to the aqueous solution (I) is not particularly limited, but it is preferable that the total molar number of zinc ions is smaller than the total molar number of carbonate ions and hydrogen carbonate ions.
[0018]
If the spherical product produced by mixing the aqueous solution (I) and the aqueous solution (II) is fired at a temperature of 300 ° C. or more, dehydration and decarboxylation occur, and spherical zinc oxide can be obtained. The firing temperature may be 300 ° C. or higher, preferably 300 ° C. to 600 ° C., more preferably 350 ° C. to 500 ° C.
The firing step does not require a special atmosphere, and may be performed in an open air using a normal firing apparatus. In some cases, the firing step can be adjusted to a non-oxidizing atmosphere.
[0019]
The zinc oxide obtained by the above method has a spherical shape. The particle size can be adjusted, for example, by appropriately setting the stirring speed of the aqueous solution (I) when the aqueous solution (II) is dropped. The particle diameter of the spherical particles is usually about 0.01 to 10 μm.
[0020]
The spherical zinc oxide of the present invention can be used, for example, as an ultraviolet absorber, a conductive material, a catalyst carrier, a reinforcing agent, a filler, a pigment, a vulcanization accelerator, and the like. Applications include paints, inks, paints, glass, glaze, plating, water repellents, dental cement, gas sensors, pharmaceuticals, petroleum refining, batteries, electrophotographic materials, phosphors, electromagnetic wave absorbers, sound absorbers, etc. Can be
In particular, since the zinc oxide of the present invention has a spherical shape and thus has a high ultraviolet protection performance, a remarkable improvement in performance is expected depending on the intended use. For example, when the zinc oxide of the present invention is used in combination with a resin or the like as a UV protection material, the spherical zinc oxide itself has a high UV protection performance, and thus has a sufficient UV protection performance in a smaller amount than flake zinc oxide or the like. Can be expected.
When the zinc oxide of the present invention is used for various applications as described above, various treatments can be applied to the extent that the spherical shape is not impaired.
[0021]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples.
[0022]
(Example 1)
200 ml of a 0.2 mol / l zinc chloride aqueous solution having a pH of 1 was gradually added dropwise to 400 ml of a 1.5 mol / l aqueous solution of ammonium hydrogen carbonate. The temperature of the aqueous solution of ammonium bicarbonate was 20 ° C.
The product thus obtained was washed, filtered and calcined at 400 ° C. Observation of the shape of the obtained zinc oxide using a scanning electron microscope (manufactured by JEOL Ltd .: JSM5301LV) revealed that the particles were spherical particles close to a true sphere (FIG. 1).
[0023]
(Example 2)
200 ml of a 0.2 mol / l zinc chloride aqueous solution having a pH of 1 was gradually added dropwise to 400 ml of a 1.5 mol / l aqueous solution of ammonium hydrogen carbonate. The temperature of the aqueous solution of ammonium bicarbonate was 40 ° C.
The product thus obtained was washed, filtered and calcined at 400 ° C. The shape of the obtained zinc oxide was confirmed to be spherical particles close to a true sphere (FIG. 2).
[0024]
(Example 3)
200 ml of a 0.2 mol / l aqueous solution of zinc chloride having a pH of 1 was gradually added dropwise to 400 ml of an aqueous 1.5 mol / l ammonium carbonate solution. The temperature of the aqueous ammonium carbonate solution was 20 ° C.
The product thus obtained was washed, filtered and calcined at 400 ° C. The shape of the obtained zinc oxide was confirmed to be spherical particles close to a true sphere (FIG. 3).
[0025]
(Comparative Example 1)
200 ml of a 0.2 mol / l zinc chloride aqueous solution having a pH of 3 was gradually added dropwise to 400 ml of a 1.5 mol / l aqueous solution of ammonium hydrogen carbonate. The temperature of the aqueous solution of ammonium bicarbonate was 40 ° C.
The product thus obtained was washed, filtered and calcined at 400 ° C. The shape of the obtained zinc oxide was sea urchin-like, and spherical zinc oxide could not be obtained.
[0026]
(Comparative Example 2)
When 200 ml of a 0.2 mol / l aqueous solution of zinc chloride having a pH of 3 was gradually added dropwise to 400 ml of a 1.5 mol / l aqueous ammonium solution, a spherical product could not be obtained.
[0027]
【The invention's effect】
According to the present invention, spherical zinc oxide having a shape close to a true sphere can be obtained.
In the manufacturing process, the synthesis temperature and the sintering temperature are low, and the zinc oxide having a spherical shape can be efficiently synthesized without almost any other zinc oxide.
[Brief description of the drawings]
FIG. 1 is an electron micrograph of spherical zinc oxide synthesized in Example 1.
FIG. 2 is an electron micrograph of spherical zinc oxide synthesized in Example 2.
FIG. 3 is an electron micrograph of spherical zinc oxide synthesized in Example 3.
Claims (2)
水溶液（Ｉ）における炭酸イオンと炭酸水素イオンの合計イオン濃度よりも、水溶液（ＩＩ）における亜鉛イオン濃度を低く設定し、かつ、水溶液（ＩＩ）のｐＨを２未満とすることを特徴とする球状酸化亜鉛の製造方法。A method for producing zinc oxide, comprising mixing an aqueous solution (I) containing carbonate ions and / or bicarbonate ions and ammonium ions with an aqueous solution (II) containing zinc ions and calcining the obtained product at 300 ° C. or higher. And
A spherical shape wherein the zinc ion concentration in the aqueous solution (II) is set lower than the total ion concentration of carbonate ions and hydrogen carbonate ions in the aqueous solution (I), and the pH of the aqueous solution (II) is less than 2. A method for producing zinc oxide.
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| JP2002310617A JP4017497B2 (en) | 2002-10-25 | 2002-10-25 | Method for producing spherical zinc oxide |
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