JPH10120418A - Production of ultrafine zinc oxide - Google Patents
Production of ultrafine zinc oxideInfo
- Publication number
- JPH10120418A JPH10120418A JP27218696A JP27218696A JPH10120418A JP H10120418 A JPH10120418 A JP H10120418A JP 27218696 A JP27218696 A JP 27218696A JP 27218696 A JP27218696 A JP 27218696A JP H10120418 A JPH10120418 A JP H10120418A
- Authority
- JP
- Japan
- Prior art keywords
- continuously
- zinc oxide
- zinc
- reaction tank
- semi
- 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
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- Cosmetics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は紫外線遮蔽性及び可
視光線透過性に優れた超微細酸化亜鉛の製造方法に関す
るものであり、さらに詳しくは、樹脂製品、化粧品、塗
料、インキ等に配合して用いるのに適した、紫外線遮蔽
性及び可視光線透過性に優れた超微細酸化亜鉛の製造方
法、或いはその上に貯蔵安定性、分散性に優れた被覆超
微細酸化亜鉛の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing ultra-fine zinc oxide having excellent ultraviolet ray shielding properties and visible light transmittance, and more particularly, to a method of formulating it in resin products, cosmetics, paints, inks and the like. The present invention relates to a method for producing ultrafine zinc oxide having excellent ultraviolet shielding properties and visible light transmittance suitable for use, or a method for producing a coated ultrafine zinc oxide having excellent storage stability and dispersibility thereon. .
【０００２】[0002]
【従来の技術】紫外線、特に３００〜４００ｎｍの波長
を有する紫外線は皮膚に対して日焼け現象を引き起し、
黒色化や炎症等の原因となる。また、この紫外線は樹脂
製品、化粧品、塗料、インキ等中に含まれるマトリック
ス樹脂、油脂を分解したり、また色素を分解し退色させ
たり、あるいは油脂、香料を酸化させ、変質、変臭を生
じさせることもある。2. Description of the Related Art Ultraviolet light, particularly ultraviolet light having a wavelength of 300 to 400 nm, causes a sunburn phenomenon on the skin,
It causes blackening and inflammation. In addition, this ultraviolet ray decomposes matrix resin and oils and fats contained in resin products, cosmetics, paints, inks, etc., decomposes and discolors pigments, or oxidizes oils and fats and fragrances, causing deterioration and odor. In some cases.
【０００３】そこで、これらの問題を解決するために紫
外線遮蔽剤を用いることが試みられている。従来、この
紫外線遮蔽剤として超微細酸化チタンが知られている。
酸化チタンは紫外線領域ではその遮蔽効果が優れている
ものの、可視光線領域では酸化チタンの屈折率（２．６
１〜２．９０、ルチル型）が酸化亜鉛の屈折率（２．０
０〜２．０２）よりも大きいため、透過率が劣る。その
ため、この酸化チタンを樹脂製品、塗料、化粧品等の透
明性材料に配合した場合に、不透明な白色を呈すること
となる。この他、酸化亜鉛に比べて紫外線照射によりマ
トリックスが変質しやすいという欠点を有する。[0003] In order to solve these problems, it has been attempted to use an ultraviolet shielding agent. Conventionally, ultrafine titanium oxide has been known as this ultraviolet shielding agent.
Although titanium oxide has an excellent shielding effect in the ultraviolet region, it has a refractive index (2.6) in the visible light region.
1-2.90, rutile type) has a refractive index (2.0) of zinc oxide.
0 to 2.02), the transmittance is inferior. For this reason, when this titanium oxide is blended with a transparent material such as a resin product, a paint, or a cosmetic, it will have an opaque white color. In addition, there is a drawback that the matrix is easily deteriorated by ultraviolet irradiation as compared with zinc oxide.
【０００４】また、その他の遮蔽剤として超微細酸化亜
鉛を用いることが報告されている。即ち、特開平２−２
０８３６９号公報には、金属亜鉛蒸気に空気を吹き付け
て酸化して得た比表面積が２５ｍ2 ／ｇの酸化亜鉛を紫
外線遮蔽剤として用いることが提案されており、その紫
外線領域における遮蔽効果と可視光線領域での透過率に
ついて言及している。しかし、そのような製造方法は高
温を必要とするので超微細酸化亜鉛を容易に且つ安価に
製造することはできず、またそのような超微細酸化亜鉛
を用いた場合にも、紫外線領域における遮蔽効果及び可
視光線領域における透過率は必ずしも満足できるもので
はなかった。It has been reported that ultrafine zinc oxide is used as another shielding agent. That is, Japanese Patent Laid-Open No. 2-2
No. 08369 proposes to use zinc oxide having a specific surface area of 25 m 2 / g obtained by blowing and oxidizing metallic zinc vapor with air as an ultraviolet shielding agent. Reference is made to the transmittance in the light beam range. However, such a manufacturing method requires high temperatures, so that ultrafine zinc oxide cannot be easily and inexpensively manufactured. In addition, even when such ultrafine zinc oxide is used, shielding in the ultraviolet region is difficult. The effect and the transmittance in the visible light region were not always satisfactory.
【０００５】一方、特開平６２−２７５１８２号公報に
は、アルミニウムや鉄等の金属と亜鉛との複合酸化物か
らなる紫外線遮蔽剤が記載されている。これらの紫外線
遮蔽剤を用いることによって紫外線に対する優れた遮蔽
能力と可視光線に対する高い透過率が得られる。しかし
ながら、これらの紫外線遮蔽剤は、初期には紫外線に対
する優れた遮蔽能力と可視光線に対する高い透過率を有
するものの、これらの特性が経時劣化し、貯蔵安定性に
劣るという課題を有する。従って、この紫外線遮蔽剤
は、長期に亘って使用することができず、実用性に欠け
るという問題を有する。On the other hand, Japanese Patent Application Laid-Open No. 62-275182 describes an ultraviolet shielding agent comprising a composite oxide of zinc with a metal such as aluminum or iron. By using these ultraviolet shielding agents, an excellent ultraviolet shielding ability and a high transmittance to visible light can be obtained. However, although these ultraviolet shielding agents initially have an excellent ultraviolet shielding ability and a high transmittance to visible light, they have the problem that their properties deteriorate with time and storage stability is poor. Therefore, this ultraviolet shielding agent has a problem that it cannot be used for a long period of time and lacks practicality.
【０００６】[0006]
【発明が解決しようとする課題】本発明はこのような従
来技術の課題を解決するためになされたものであり、本
発明の目的は、紫外線に対する優れた遮蔽能力を有する
と共に、可視光線に対する高い透過率をもバランスよく
有し、しかもこれらの特性が経時劣化しない超微細酸化
亜鉛、好ましくは比表面積（本明細書において比表面積
はＢＥＴ法により測定した値である）が３０〜１００ｍ
2/ｇである超微細酸化亜鉛を容易に且つ安価に製造する
ことのできる製造方法を提供することにある。本発明の
その他の目的は、紫外線に対する優れた遮蔽能力を有す
ると共に、可視光線に対する高い透過率をもバランスよ
く有し、しかもこれらの特性が経時劣化せず、特に貯蔵
安定性、分散性に優れた超微細酸化亜鉛を容易に且つ安
価に製造することのできる方法を提供することにある。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and an object of the present invention is to have an excellent ultraviolet light shielding ability and a high visible light shielding ability. Ultrafine zinc oxide having a well-balanced transmittance and not deteriorating these properties over time, preferably having a specific surface area (in this specification, the specific surface area is a value measured by the BET method) of 30 to 100 m
It is an object of the present invention to provide a method for easily and inexpensively producing ultrafine zinc oxide of 2 / g. Another object of the present invention is to have excellent shielding ability against ultraviolet light, high transmittance to visible light in a well-balanced manner, and these properties do not deteriorate over time, and particularly, excellent storage stability and dispersibility. Another object of the present invention is to provide a method capable of easily and inexpensively producing ultrafine zinc oxide.
【０００７】[0007]
【課題を達成するための手段】本発明者は、上記の目的
を達成するために種々検討の結果、反応槽を連続的に特
定の回転速度で高速撹拌しながら亜鉛塩水溶液とアルカ
リ水溶液とを特定の条件下で反応させ、反応で生じる中
和生成物を濾過、洗浄し、次いで乾燥、焼成するること
により上記目的が達成されること、更に生成酸化亜鉛を
シリコーンオイル又は脂肪酸で表面処理することにより
特に貯蔵安定性、分散性に優れた超微細酸化亜鉛が得ら
れることを見いだし、本発明を完成した。即ち、本発明
の超微細酸化亜鉛の製造方法は、亜鉛塩水溶液とアルカ
リ水溶液とを亜鉛：アルカリの当量比が１：１〜１：３
となる量比で、それぞれ別々にかつ同時に、連続的に又
は半連続的に反応槽に装入し、反応槽を連続的に２００
０〜２００００ｒｐｍの回転速度で高速撹拌し、反応で
生じる中和生成物を連続的に又は半連続的に反応槽から
取り出し、その後濾過、洗浄し、次いで乾燥、焼成する
ことを特徴とする。Means for Achieving the Object As a result of various studies to achieve the above object, the present inventor has found that a zinc salt aqueous solution and an alkaline aqueous solution are mixed while continuously stirring the reaction vessel at a specific rotation speed at a high speed. The above-mentioned object is achieved by reacting under specific conditions, filtering and washing the neutralized product generated by the reaction, followed by drying and calcining. Further, the produced zinc oxide is surface-treated with silicone oil or fatty acid. As a result, it has been found that ultrafine zinc oxide having particularly excellent storage stability and dispersibility can be obtained, and the present invention has been completed. That is, in the method for producing ultrafine zinc oxide of the present invention, a zinc salt aqueous solution and an alkaline aqueous solution are mixed at a zinc: alkali equivalent ratio of 1: 1 to 1: 3.
Are charged separately and simultaneously, continuously or semi-continuously to the reaction tank, and the reaction tank is continuously charged for 200 times.
It is characterized in that high-speed stirring is performed at a rotation speed of 0 to 20,000 rpm, a neutralized product generated in the reaction is continuously or semi-continuously removed from the reaction tank, and then filtered, washed, dried, and calcined.
【０００８】また、本発明の被覆超微細酸化亜鉛の製造
方法は、亜鉛塩水溶液とアルカリ水溶液とを亜鉛：アル
カリの当量比が１：１〜１：３となる量比で、それぞれ
別々にかつ同時に、連続的に又は半連続的に反応槽に装
入し、反応槽を連続的に２０００〜２００００ｒｐｍの
回転速度で高速撹拌し、反応で生じる中和生成物を連続
的に又は半連続的に反応槽から取り出し、その後濾過、
洗浄し、次いで乾燥、焼成した後、シリコーンオイル又
は脂肪酸で表面処理することを特徴とする。Further, in the method for producing a coated ultrafine zinc oxide according to the present invention, the aqueous zinc salt solution and the aqueous alkaline solution are separately and separately provided at an equivalent ratio of zinc: alkali of 1: 1 to 1: 3. At the same time, the reaction vessel is continuously or semi-continuously charged into the reaction vessel, and the reaction vessel is continuously stirred at a high speed at a rotation speed of 2000 to 20000 rpm to continuously or semi-continuously neutralize the reaction product. Removed from the reaction tank, then filtered,
It is characterized in that it is washed, then dried and calcined and then surface-treated with silicone oil or fatty acid.
【０００９】以下、本発明の製造方法を具体的に説明す
る。本発明で使用する亜鉛塩水溶液は硫酸亜鉛、塩化亜
鉛、硝酸亜鉛等を水に溶解させて調製することができ
る。この水溶液は所望により少量の酸を含有していても
よい。また、本発明で使用するアルカリ水溶液はアルカ
リ金属の水酸化物水溶液、アルカリ金属の炭酸塩水溶
液、アルカリ金属のシュウ酸塩水溶液等である。上記の
亜鉛塩及びアルカリはいずれも市販品をそのまま用いる
ことができる。Hereinafter, the production method of the present invention will be specifically described. The aqueous zinc salt solution used in the present invention can be prepared by dissolving zinc sulfate, zinc chloride, zinc nitrate and the like in water. This aqueous solution may optionally contain a small amount of acid. The aqueous alkali solution used in the present invention is an aqueous alkali metal hydroxide solution, an aqueous alkali metal carbonate solution, an aqueous alkali metal oxalate solution, or the like. As the above zinc salt and alkali, commercially available products can be used as they are.
【００１０】本発明においては、これらの亜鉛塩水溶液
は好ましくは０．０１〜１０Ｍ（モル濃度、mol/l ）の
濃度で用い、一層良好な生産効率を達成し且つ一層狭い
範囲の粒度分布を有する一層微細な酸化亜鉛を得るため
には、より好ましくは１〜５Ｍの濃度で用い、また、ア
ルカリ水溶液は好ましくは０．０１〜１０Ｍの濃度で用
い、一層良好な生産効率を達成し且つ一層狭い範囲の粒
度分布を有する一層微細な酸化亜鉛を得るためには、よ
り好ましくは０．１〜１０Ｍの濃度で用いる。亜鉛塩及
びアルカリの水溶液の濃度が０．０１未満である場合に
は生産効率が低下する傾向があり、また１０Ｍを超える
場合には生成酸化亜鉛粒子が粗大化し易く、超微細粒子
を得ることが困難になる傾向がある。In the present invention, these aqueous zinc salt solutions are preferably used at a concentration of 0.01 to 10 M (molar concentration, mol / l) to achieve better production efficiency and to achieve a narrower particle size distribution. In order to obtain finer zinc oxide, more preferably, it is used at a concentration of 1 to 5 M, and the alkaline aqueous solution is preferably used at a concentration of 0.01 to 10 M to achieve better production efficiency and To obtain a finer zinc oxide having a narrow range of particle size distribution, it is more preferably used at a concentration of 0.1 to 10M. If the concentration of the aqueous solution of the zinc salt and the alkali is less than 0.01, the production efficiency tends to decrease, and if it exceeds 10M, the generated zinc oxide particles are liable to become coarse and ultrafine particles can be obtained. Tends to be difficult.
【００１１】本発明においては、流量調整可能なポンプ
を用いて亜鉛塩水溶液とアルカリ水溶液とを亜鉛：アル
カリの当量比が１：１〜１：３となる量比で、それぞれ
別々にかつ同時に、連続的に又は半連続的に反応槽に装
入する。反応槽に装入する亜鉛：アルカリの当量比が
１：１よりも大きい場合、即ち亜鉛の量が当量よりも多
い場合には、酸化亜鉛の粒子が粗大化し易く、超微細粒
子を得ることが困難になる傾向があるので好ましくな
い。また、亜鉛：アルカリの当量比が１：３よりも小さ
い場合、即ち亜鉛の量が当量の３分の１よりも少ない場
合には、生産効率が低下する傾向があるので好ましくな
い。In the present invention, the aqueous zinc salt solution and the aqueous alkaline solution are separately and simultaneously used in a quantitative ratio of 1: 1 to 1: 3 by using a pump capable of adjusting the flow rate. The reactor is charged continuously or semi-continuously. When the equivalent ratio of zinc: alkali charged in the reaction tank is larger than 1: 1, that is, when the amount of zinc is larger than the equivalent, the zinc oxide particles are likely to coarsen, and ultrafine particles may be obtained. It is not preferable because it tends to be difficult. If the zinc: alkali equivalent ratio is less than 1: 3, that is, if the amount of zinc is less than one third of the equivalent, the production efficiency tends to decrease, which is not preferable.
【００１２】本発明においては、亜鉛塩水溶液とアルカ
リ水溶液とをそれぞれ別々にかつ同時に反応槽に装入す
るので、反応温度及びｐＨはほぼ一定値に保持される。
本発明においては、亜鉛塩水溶液とアルカリ水溶液とを
亜鉛：アルカリの当量比が１：１〜１：３となる量比
で、それぞれ別々にかつ同時に反応槽に装入する限りは
連続的に装入し且つ連続的に取り出してもよく、或いは
反応槽中の中和生成物含有分散液の一定量（例えば半分
量）を取り出し、取り出しを停止した後亜鉛塩水溶液と
アルカリ水溶液とを亜鉛：アルカリの当量比が１：１〜
１：３となる量比で、それぞれ別々にかつ同時に、反応
槽に所定量になるまで徐々に追加装入し、所定時間の後
反応槽中の中和生成物含有分散液の一定量を取り出すこ
とを繰り返し実施しても、即ち半連続的に実施してもよ
い。このように半連続的に実施することにより、反応槽
から中和生成物含有分散液を取り出す際に未反応の亜鉛
塩が一緒に取り出される危険性がなく、従って、取り出
した後に生成粒子が粗大化する危険性はない。In the present invention, since the aqueous zinc salt solution and the aqueous alkaline solution are separately and simultaneously charged into the reaction tank, the reaction temperature and the pH are maintained at substantially constant values.
In the present invention, the aqueous zinc salt solution and the aqueous alkaline solution are continuously charged at a ratio of zinc: alkali equivalent ratio of 1: 1 to 1: 3 as long as they are separately and simultaneously charged into the reaction vessel. Alternatively, a certain amount (for example, half) of the neutralized product-containing dispersion in the reaction vessel may be taken out and taken out, and after stopping the taking out, a zinc salt aqueous solution and an alkaline aqueous solution may be mixed with zinc: alkali. The equivalent ratio of 1: 1 to 1
At a volume ratio of 1: 3, separately and simultaneously, gradually and additionally, until the predetermined amount is added to the reaction tank, and after a predetermined time, a certain amount of the neutralized product-containing dispersion in the reaction tank is taken out. This may be performed repeatedly, that is, performed semi-continuously. By carrying out semi-continuously in this manner, there is no danger that unreacted zinc salt is taken out together when the dispersion containing the neutralized product is taken out of the reaction tank, and thus the product particles are coarse after being taken out. There is no danger of conversion.
【００１３】反応槽では中和反応によって中和生成物が
析出する。この際に、超微細酸化亜鉛を得るためには高
速撹拌を行なうことが必須であり、２０００〜２０００
０ｒｐｍの高速均一撹拌を実施する。中和反応によって
析出した中和生成物がこのような高速撹拌によって瞬時
に拡散され、粒子の粗大化が抑制され、超微細粒子化が
促進される。攪拌速度が２０００ｒｐｍ未満の場合には
粒子の成長が速くなって粗粒子の生成比率が高くなり、
所望の超微細粒子を得ることが困難になる。また、２０
０００ｒｐｍよりも速い場合には反応液の流れが攪拌翼
から離れて攪拌効果が低下するので、２００００ｒｐｍ
よりも速くしても意味がない。このような攪拌は、例え
ばインペラーミルでも、インラインミキサーでもよい。In the reaction tank, a neutralized product is precipitated by the neutralization reaction. At this time, high-speed stirring is indispensable in order to obtain ultrafine zinc oxide.
Perform high-speed uniform stirring at 0 rpm. The neutralized product precipitated by the neutralization reaction is instantaneously diffused by such high-speed stirring, so that coarsening of the particles is suppressed and ultrafine particles are promoted. When the stirring speed is less than 2000 rpm, the growth of the particles becomes faster and the generation ratio of the coarse particles becomes higher,
It becomes difficult to obtain the desired ultrafine particles. Also, 20
If the rotation speed is higher than 2,000 rpm, the flow of the reaction solution is separated from the stirring blade and the stirring effect is reduced.
There is no point in making it faster. Such stirring may be performed by, for example, an impeller mill or an in-line mixer.
【００１４】上記のような条件下での中和反応によって
中和生成物を析出させることにより安定した操業が可能
であり、大量生産する場合にも品質が安定しており、比
表面積が３０〜１００ｍ2/ｇである超微細酸化亜鉛が得
られる。上記のような連続的な又は半連続的な操作にお
いては、中和生成物含有分散液を、例えば反応槽の下部
から連続的に又は半連続的に徐々に取り出す。取り出し
た中和生成物含有分散液を固液分離、濾過、洗浄、乾燥
し、更に３００〜１０００℃、好ましくは３５０〜７０
０℃の温度範囲で、大気圧下又は減圧下（１０ｍｍＨｇ
以下）にて２〜３時間の焼成を行なう。The stable operation is possible by precipitating the neutralized product by the neutralization reaction under the above conditions, and the quality is stable even in mass production, and the specific surface area is 30 to 50%. An ultrafine zinc oxide of 100 m 2 / g is obtained. In the continuous or semi-continuous operation as described above, the dispersion containing the neutralized product is gradually removed, for example, continuously or semi-continuously from the lower part of the reaction vessel. The neutralized product-containing dispersion taken out is subjected to solid-liquid separation, filtration, washing, and drying, and further subjected to 300 to 1000C, preferably 350 to 70C.
In a temperature range of 0 ° C. under atmospheric pressure or reduced pressure (10 mmHg
In the following, baking is performed for 2 to 3 hours.
【００１５】このようにして得られる超微細酸化亜鉛は
表面が非常に活性であるので、貯蔵安定性、分散性を向
上させ、また樹脂製品、塗料、化粧品等に配合した場合
のマトリックス又は他の添加剤との反応を防止する目的
で、所望により、シリコーンオイルや脂肪酸で表面処理
することができる。具体的な処理方法としては、シリコ
ーンオイルや脂肪酸をメタノール、エタノール等のアル
コール類、もしくはアセトン、メチルエチルケトン等の
ケトン類等の有機溶媒に溶解し、この溶液に酸化亜鉛を
直接浸漬するか、あるいは酸化亜鉛にスプレーすること
により実施できる。このような処理を行なった後、８０
〜１５０℃で酸化亜鉛を再度乾燥させる。The ultrafine zinc oxide thus obtained has a very active surface, so that it has improved storage stability and dispersibility, and can be used as a matrix or other material when blended in resin products, paints, cosmetics and the like. For the purpose of preventing the reaction with the additive, the surface can be treated with a silicone oil or a fatty acid, if desired. As a specific treatment method, a silicone oil or a fatty acid is dissolved in an organic solvent such as an alcohol such as methanol or ethanol, or a ketone such as acetone or methyl ethyl ketone, and zinc oxide is directly immersed in the solution or oxidized. This can be done by spraying on zinc. After performing such processing, 80
Dry the zinc oxide again at ~ 150 ° C.
【００１６】表面処理に用いることのできるシリコーン
オイルとしてはジメチルシリコーンオイル、メチルフェ
ニルシリコーンオイル、環状シリコーンオイル、ポリエ
ーテルシリコーンオイル、変性シリコーンオイル、メチ
ルハイドロジエンシリコーンオイル等が例示される。ま
た、脂肪酸としてはｎ−デカン酸、カプリル酸、ラウリ
ン酸、ステアリン酸、ベヘン酸、パルミチン酸等の飽和
脂肪酸やリノール酸、リノレイン酸、オレイン酸等の不
飽和脂肪酸が例示される。これらのシリコーンオイルや
脂肪酸の処理量（被覆量）は酸化亜鉛の重量に基づいて
０．０５〜１０重量％となるような量が望ましい。Examples of the silicone oil that can be used for the surface treatment include dimethyl silicone oil, methylphenyl silicone oil, cyclic silicone oil, polyether silicone oil, modified silicone oil, and methyl hydrogen silicone oil. Examples of the fatty acid include saturated fatty acids such as n-decanoic acid, caprylic acid, lauric acid, stearic acid, behenic acid, and palmitic acid, and unsaturated fatty acids such as linoleic acid, linoleic acid, and oleic acid. The treatment amount (coating amount) of these silicone oils and fatty acids is desirably 0.05 to 10% by weight based on the weight of zinc oxide.
【００１７】本発明の製造方法によって得られる超微細
酸化亜鉛は優れた紫外線遮蔽効果を有し、可視光線領域
においての透過率が高く、また表面処理を行なった被覆
超微細酸化亜鉛は、樹脂製品、塗料、化粧品等に配合し
た場合にもマトリックスや添加剤と反応することはな
く、また貯蔵安定性、分散性が向上し、優れた紫外線遮
蔽効果と可視光線領域においての高い透過率を長期に亘
って維持できる。The ultrafine zinc oxide obtained by the production method of the present invention has an excellent ultraviolet shielding effect, a high transmittance in the visible light region, and a coated ultrafine zinc oxide which has been subjected to surface treatment is a resin product. It does not react with matrix or additives even when blended in paints, cosmetics, etc., improves storage stability and dispersibility, and has excellent UV shielding effect and high transmittance in the visible light region for a long time. Can be maintained throughout.
【００１８】[0018]
【実施例】以下、本発明を実施例に基づいて具体的に説
明する。 実施例１ ３Ｍの塩化亜鉛水溶液及び１Ｍの炭酸ナトリウム水溶液
を準備した。その塩化亜鉛水溶液及び炭酸ナトリウム水
溶液を各々流量調整可能なポンプで亜鉛：アルカリの当
量比が１：２になるように流量を調整して反応槽に同時
に別個に連続送液し、反応槽内をインペラーミルで６０
００ｒｐｍの回転速度で高速攪拌して中和生成物を析出
させた。この間、特に加温は行なわず、ｐＨ６〜８に維
持した。また、反応槽への送液量と同量を反応槽から連
続的に取り出した。中和生成物含有分散液の濾過、洗浄
を、その濾液導電率が２００μｓ／ｃｍ以下になるまで
繰返し、得られたケーキを１５０℃で乾燥した。その
後、空気中４００℃で３ｈｒの焼成を行なって、比表面
積が５０ｍ2/ｇである超微細酸化亜鉛を得た。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments. Example 1 A 3M aqueous zinc chloride solution and a 1M aqueous sodium carbonate solution were prepared. The zinc chloride aqueous solution and the sodium carbonate aqueous solution are separately and continuously fed into the reaction tank simultaneously by adjusting the flow rate so that the equivalent ratio of zinc: alkali becomes 1: 2 by a pump capable of adjusting the flow rate. 60 with impeller mill
High-speed stirring was performed at a rotation speed of 00 rpm to precipitate a neutralized product. During this time, no particular heating was performed, and the pH was maintained at 6 to 8. Further, the same amount as the amount of liquid sent to the reaction tank was continuously taken out of the reaction tank. The filtration and washing of the neutralized product-containing dispersion were repeated until the filtrate conductivity became 200 μs / cm or less, and the obtained cake was dried at 150 ° C. Thereafter, firing was performed in air at 400 ° C. for 3 hours to obtain ultrafine zinc oxide having a specific surface area of 50 m 2 / g.
【００１９】この酸化亜鉛の粉末をポリエステル系樹脂
に３０重量％配合し、ガラスビーズと共にペイントシエ
ーカーで１．５時間分散し、バーコーターにてＯＨＰシ
ートに塗布し、７０〜８０℃で乾燥して透明塗布膜を得
た。得られた透明塗布膜について、日本電色工業社製濁
度計によって可視光線領域（４００〜７００ｎｍ）の透
過率を測定したところ、９２％であった。また、同様に
日立社製分光光度計にて紫外線領域（３８０ｎｍ）の透
過率を測定したところ、６％であった。なお、酸化亜鉛
の粉末を配合しなかった以外は上記と同様にして得た透
明塗布膜について、上記と同様にして可視光線透過率を
測定したところ、９８％であった。また、同様に紫外線
透過率を測定したところ、９８％であった。This zinc oxide powder was mixed with a polyester resin at 30% by weight, dispersed with glass beads in a paint shaker for 1.5 hours, applied to an OHP sheet with a bar coater, and dried at 70 to 80 ° C. Thus, a transparent coating film was obtained. The transmittance of the obtained transparent coating film in the visible light region (400 to 700 nm) was measured with a turbidimeter manufactured by Nippon Denshoku Industries Co., Ltd., and was 92%. Similarly, the transmittance in the ultraviolet region (380 nm) was measured with a spectrophotometer manufactured by Hitachi, Ltd., and found to be 6%. The visible light transmittance of the transparent coating film obtained in the same manner as described above except that no zinc oxide powder was blended was 98%. In addition, when the ultraviolet transmittance was measured in the same manner, it was 98%.
【００２０】実施例２ ３Ｍの硫酸亜鉛水溶液及び１Ｍの炭酸ナトリウム水溶液
を準備した。その塩化亜鉛水溶液及び炭酸ナトリウム水
溶液を各々流量調整可能なポンプで亜鉛：アルカリの当
量比が１：２になるように流量を調整して反応槽に同時
に別個に連続送液し、反応槽内をインペラーミルで６０
００ｒｐｍの回転速度で高速攪拌して中和生成物を析出
させた。この間、特に加温は行なわず、ｐＨ６〜８に維
持した。また、反応槽への送液量と同量を反応槽から連
続的に取り出した。中和生成物含有分散液の濾過、洗浄
を、その濾液導電率が２００μｓ／ｃｍ以下になるまで
繰返し、得られたケーキを１５０℃で乾燥した。その
後、空気中４００℃で３ｈｒの焼成を行なって、比表面
積が６５ｍ2/ｇである超微細酸化亜鉛を得た。Example 2 A 3M aqueous solution of zinc sulfate and a 1M aqueous solution of sodium carbonate were prepared. The zinc chloride aqueous solution and the sodium carbonate aqueous solution are separately and continuously fed into the reaction tank simultaneously by adjusting the flow rate so that the equivalent ratio of zinc: alkali becomes 1: 2 by a pump capable of adjusting the flow rate. 60 with impeller mill
High-speed stirring was performed at a rotation speed of 00 rpm to precipitate a neutralized product. During this time, no particular heating was performed, and the pH was maintained at 6 to 8. Further, the same amount as the amount of liquid sent to the reaction tank was continuously taken out of the reaction tank. The filtration and washing of the neutralized product-containing dispersion were repeated until the filtrate conductivity became 200 μs / cm or less, and the obtained cake was dried at 150 ° C. Thereafter, firing was performed in air at 400 ° C. for 3 hours to obtain ultrafine zinc oxide having a specific surface area of 65 m 2 / g.
【００２１】この酸化亜鉛の粉末をポリエステル系樹脂
に３０重量％配合し、ガラスビーズと共にペイントシエ
ーカーで１．５時間分散し、バーコーターにてＯＨＰシ
ートに塗布し、７０〜８０℃で乾燥して透明塗布膜を得
た。得られた透明塗布膜について、実施例１と同様にし
て可視光線透過率を測定したところ、９３％であった。
また、同様に紫外線透過率を測定したところ、５％であ
った。This zinc oxide powder was mixed with a polyester resin at 30% by weight, dispersed with glass beads in a paint shaker for 1.5 hours, applied to an OHP sheet with a bar coater, and dried at 70 to 80 ° C. Thus, a transparent coating film was obtained. When the visible light transmittance of the obtained transparent coating film was measured in the same manner as in Example 1, it was 93%.
The UV transmittance was measured in the same manner and found to be 5%.
【００２２】実施例３ ３Ｍの塩化亜鉛水溶液及び１Ｍのシュウ酸ナトリウム水
溶液を準備した。その塩化亜鉛水溶液及び炭酸ナトリウ
ム水溶液を各々流量調整可能なポンプで亜鉛：アルカリ
の当量比が１：２になるように流量を調整して反応槽に
同時に別個に連続送液し、反応槽内をインペラーミルで
６０００ｒｐｍの回転速度で高速攪拌して中和生成物を
析出させた。この間、特に加温は行なわず、ｐＨ６〜８
に維持した。また、反応槽への送液量と同量を反応槽か
ら連続的に取り出した。中和生成物含有分散液の濾過、
洗浄を、その濾液導電率が２００μｓ／ｃｍ以下になる
まで繰返し、得られたケーキを１５０℃で乾燥した。そ
の後、空気中４００℃で３ｈｒの焼成を行なって、比表
面積が１００ｍ2/ｇである超微細酸化亜鉛を得た。Example 3 A 3M aqueous solution of zinc chloride and a 1M aqueous solution of sodium oxalate were prepared. The zinc chloride aqueous solution and the sodium carbonate aqueous solution are separately and continuously fed into the reaction tank simultaneously by adjusting the flow rate so that the equivalent ratio of zinc: alkali becomes 1: 2 by a pump capable of adjusting the flow rate. The neutralized product was precipitated by high-speed stirring at a rotation speed of 6000 rpm using an impeller mill. During this time, no special heating was performed, and the pH was 6 to 8
Maintained. Further, the same amount as the amount of liquid sent to the reaction tank was continuously taken out of the reaction tank. Filtration of the neutralized product-containing dispersion,
Washing was repeated until the filtrate conductivity became 200 μs / cm or less, and the obtained cake was dried at 150 ° C. Thereafter, firing was performed in air at 400 ° C. for 3 hours to obtain ultrafine zinc oxide having a specific surface area of 100 m 2 / g.
【００２３】この酸化亜鉛の粉末をポリエステル系樹脂
に３０重量％配合し、ガラスビーズと共にペイントシエ
ーカーで１．５時間分散し、バーコーターにてＯＨＰシ
ートに塗布し、７０〜８０℃で乾燥して透明塗布膜を得
た。得られた透明塗布膜について、実施例１と同様にし
て日本電色工業社製濁度計によって可視光線領域（４０
０〜７００ｎｍ）の透過率を測定したところ、９４％で
あった。また、同様に日立社製分光光度計にて紫外線領
域（３８０ｎｍ）の透過率を測定したところ、４％であ
った。This zinc oxide powder was mixed with a polyester resin at 30% by weight, dispersed with glass beads in a paint shaker for 1.5 hours, applied to an OHP sheet with a bar coater, and dried at 70 to 80 ° C. Thus, a transparent coating film was obtained. About the obtained transparent coating film, the turbidimeter manufactured by Nippon Denshoku Industries Co., Ltd.
(0-700 nm) was 94%. Similarly, the transmittance in the ultraviolet region (380 nm) was measured with a spectrophotometer manufactured by Hitachi, Ltd., and it was 4%.
【００２４】実施例４ 実施例１に記載の方法を半連続的に実施した。即ち、反
応槽中の中和生成物含有分散液の半分量を取り出し、取
り出しを停止した後３Ｍの塩化亜鉛水溶液及び１Ｍの炭
酸ナトリウム水溶液を各々流量調整可能なポンプで亜
鉛：アルカリの当量比が１：２になるように流量を調整
してそれぞれ別々にかつ同時に、反応槽に所定量になる
まで連続送液し、反応槽内をインペラーミルで６０００
ｒｐｍの回転速度で高速攪拌して中和生成物を析出さ
せ、反応槽への送液の停止から２分後に反応槽中の中和
生成物含有分散液の半分量を取り出した。この間、特に
加温は行なわず、ｐＨ６〜８に維持した。この操作を繰
り返し実施した。得られた超微細酸化亜鉛は実施例１で
得られたものと同一であった。Example 4 The method described in Example 1 was carried out semi-continuously. That is, half of the neutralized product-containing dispersion in the reaction tank is taken out, and after stopping the take-out, a 3M aqueous solution of zinc chloride and a 1M aqueous solution of sodium carbonate are supplied with a pump capable of controlling the flow rate of each zinc and the equivalent ratio of zinc: alkali. The flow rate was adjusted so as to be 1: 2, and the solution was continuously and separately supplied to the reaction tank until a predetermined amount was reached. The inside of the reaction tank was 6000 with an impeller mill.
Neutralized products were precipitated by high-speed stirring at a rotation speed of rpm, and two minutes after stopping the supply of the solution to the reaction tank, half of the neutralized product-containing dispersion in the reaction tank was taken out. During this time, no particular heating was performed, and the pH was maintained at 6 to 8. This operation was repeatedly performed. The ultrafine zinc oxide obtained was identical to that obtained in Example 1.
【００２５】実施例５ 実施例１で得た酸化亜鉛の超微細粉末をシリコーンオイ
ルで表面処理した。即ち、シリコーンオイルとして東レ
・ダウ・コーニング社製の塗料添加用シリコーンオイル
ＤＣ−３ＰＡ（純度１０％）を用い、このシリコーンオ
イル１３５ｇをトルエン５リットルに添加し、５分間撹
拌してそのシリコーンオイルのトルエン溶液を調製し
た。この溶液に実施例１で得た酸化亜鉛の超微細粉末
２．７Ｋｇを添加し、さらに３０分間撹拌した。濾過
し、１２０℃で乾燥して得た粉末は撥水性であり、シリ
コーンオイルが充分に被覆されていることが判った。ま
た、シリコーンオイルの被覆量は酸化亜鉛に対して０．
５重量％であった。Example 5 The ultrafine powder of zinc oxide obtained in Example 1 was surface-treated with silicone oil. That is, a silicone oil DC-3PA (purity: 10%) for coating addition manufactured by Dow Corning Toray Co., Ltd. was used as the silicone oil, and 135 g of this silicone oil was added to 5 liters of toluene, and the mixture was stirred for 5 minutes and stirred. A toluene solution was prepared. 2.7 kg of the ultrafine zinc oxide powder obtained in Example 1 was added to this solution, and the mixture was further stirred for 30 minutes. The powder obtained by filtration and drying at 120 ° C. was water-repellent and proved to be sufficiently coated with silicone oil. Further, the coating amount of silicone oil is 0.1% with respect to zinc oxide.
It was 5% by weight.
【００２６】この表面処理した酸化亜鉛の粉末をポリエ
ステル系樹脂に３０重量％配合し、ガラスビーズと共に
ペイントシエーカーで１．５時間分散し、バーコーター
にてＯＨＰシートに塗布し、７０〜８０℃で乾燥して透
明塗布膜を得た。得られた透明塗布膜について、実施例
１と同様にして可視光線透過率を測定したところ、９０
％であった。また、同様に紫外線透過率を測定したとこ
ろ、６％であった。また、この透明塗布膜について、温
度４０℃、相対湿度９０％の条件で２４０時間の耐環境
加速試験を行った後に、実施例１と同様にして可視光線
透過率を測定したところ、９０％であった。また、紫外
線透過率を測定したところ、６％であった。30% by weight of this surface-treated zinc oxide powder was blended with a polyester resin, dispersed with glass beads for 1.5 hours in a paint shaker, and applied to an OHP sheet with a bar coater. To obtain a transparent coating film. When the visible light transmittance of the obtained transparent coating film was measured in the same manner as in Example 1, the transmittance was 90%.
%Met. The UV transmittance was measured in the same manner and found to be 6%. The transparent coating film was subjected to an environmental resistance acceleration test for 240 hours at a temperature of 40 ° C. and a relative humidity of 90%, and the visible light transmittance was measured in the same manner as in Example 1. there were. The measured ultraviolet transmittance was 6%.
【００２７】実施例６ 実施例４で用いたシリコーンオイル１３５ｇとトルエン
５リットルの代わりにｎ−デカン酸３００ｇとメチルア
ルコール３０リットルを用いた以外は、実施例５と同様
に表面処理して酸化亜鉛の粉末を得、さらに透明塗布膜
を調製した。この透明塗布膜について、実施例１と同様
にして可視光線透過率を測定したところ、９２％であっ
た。また、同様に紫外線透過率を測定したところ、６％
であった。また、この透明塗布膜について、温度４０
℃、相対湿度９０％の条件で２４０時間の耐環境加速試
験を行った後に、実施例１と同様にして可視光線透過率
を測定したところ、９０％であった。また、紫外線透過
率を測定したところ、７％であった。Example 6 A surface treatment was carried out in the same manner as in Example 5 except that 135 g of the silicone oil and 5 L of toluene were replaced by 300 g of n-decanoic acid and 30 L of methyl alcohol. And a transparent coating film was prepared. When the visible light transmittance of this transparent coating film was measured in the same manner as in Example 1, it was 92%. When the ultraviolet transmittance was measured in the same manner, it was 6%.
Met. In addition, for this transparent coating film, a temperature of 40
After performing an environmental resistance acceleration test for 240 hours under conditions of 90 ° C. and a relative humidity of 90%, the visible light transmittance was measured in the same manner as in Example 1, and it was 90%. Further, the ultraviolet transmittance was measured and found to be 7%.
【００２８】実施例７ 実施例６で用いたｎ−デカン酸３００ｇをラウリン酸３
００ｇに変えた以外は実施例６と同様に表面処理した酸
化亜鉛の粉末を得、さらに透明塗布膜を調製した。この
透明塗布膜について、実施例１と同様にして可視光線透
過率を測定したところ、９２％であった。また、同様に
紫外線透過率を測定したところ、６％であった。また、
この透明塗布膜について、温度４０℃、相対湿度９０％
の条件で２４０時間の耐環境加速試験を行った後に、実
施例１と同様にして可視光線透過率を測定したところ、
９０％であった。また、紫外線透過率を測定したとこ
ろ、８％であった。Example 7 300 g of n-decanoic acid used in Example 6 was replaced with lauric acid 3
A zinc oxide powder surface-treated in the same manner as in Example 6 except that the amount was changed to 00 g, was obtained, and a transparent coating film was further prepared. When the visible light transmittance of this transparent coating film was measured in the same manner as in Example 1, it was 92%. The UV transmittance was measured in the same manner and found to be 6%. Also,
About this transparent coating film, a temperature of 40 ° C. and a relative humidity of 90%
After conducting an environment resistance acceleration test for 240 hours under the conditions described above, the visible light transmittance was measured in the same manner as in Example 1.
90%. The ultraviolet transmittance was measured and found to be 8%.
【００２９】[0029]
【発明の効果】以上に説明したように、本発明の製造方
法によって超微細酸化亜鉛が安定且つ均一に工業的規模
で得られ、これらの超微細酸化亜鉛は紫外線に対する優
れた遮蔽能力を有すると共に、可視光線に対する高い透
過率をもバランスよく有しており、また表面処理されて
いる場合には、貯蔵安定性が一層改善され、これらの特
性が長期に亘って維持される。また、樹脂製品、塗料、
化粧品等に配合した場合にもマトリックス等と反応を生
じることもない。As described above, according to the production method of the present invention, ultrafine zinc oxide can be obtained stably and uniformly on an industrial scale, and these ultrafine zinc oxides have excellent shielding ability against ultraviolet rays. It also has a high transmittance to visible light in a well-balanced manner, and when subjected to a surface treatment, storage stability is further improved, and these properties are maintained for a long time. Also, resin products, paints,
It does not react with the matrix or the like even when it is incorporated into cosmetics or the like.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｋ 9/04 Ｃ０８Ｋ 9/04 9/06 9/06 Ｃ０９Ｃ 1/04 Ｃ０９Ｃ 1/04 Ｃ０９Ｄ 5/00 Ｃ０９Ｄ 5/00 Ｚ 7/12 7/12 Ｚ Ｃ０９Ｋ 3/00 １０４ Ｃ０９Ｋ 3/00 １０４Ｚ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification symbol FI C08K 9/04 C08K 9/04 9/06 9/06 C09C 1/04 C09C 1/04 C09D 5/00 C09D 5/00 Z 7 / 12 7/12 Z C09K 3/00 104 C09K 3/00 104Z
Claims (3)
アルカリの当量比が１：１〜１：３となる量比で、それ
ぞれ別々にかつ同時に、連続的に又は半連続的に反応槽
に装入し、反応槽を連続的に２０００〜２００００ｒｐ
ｍの回転速度で高速撹拌し、反応で生じる中和生成物を
連続的に又は半連続的に反応槽から取り出し、その後濾
過、洗浄し、次いで乾燥、焼成することを特徴とする超
微細酸化亜鉛の製造方法。1. An aqueous zinc salt solution and an aqueous alkaline solution comprising zinc:
The equivalent ratio of alkali is 1: 1 to 1: 3, and they are separately and simultaneously, continuously or semi-continuously charged into the reaction tank, and the reaction tank is continuously 2,000 to 20,000 rpm.
ultra-fine zinc oxide, characterized in that high-speed stirring is performed at a rotation speed of m, and a neutralized product generated in the reaction is continuously or semi-continuously taken out of the reaction tank, and then filtered, washed, dried and calcined. Manufacturing method.
細酸化亜鉛を製造することを特徴とする請求項１記載の
製造方法。2. The method according to claim 1, wherein an ultrafine zinc oxide having a specific surface area of 30 to 100 m 2 / g is produced.
アルカリの当量比が１：１〜１：３となる量比で、それ
ぞれ別々にかつ同時に、連続的に又は半連続的に反応槽
に装入し、反応槽を連続的に２０００〜２００００ｒｐ
ｍの回転速度で高速撹拌し、反応で生じる中和生成物を
連続的に又は半連続的に反応槽から取り出し、その後濾
過、洗浄し、次いで乾燥、焼成した後、シリコーンオイ
ル又は脂肪酸で表面処理することを特徴とする被覆超微
細酸化亜鉛の製造方法。3. An aqueous zinc salt solution and an aqueous alkali solution comprising zinc:
The equivalent ratio of alkali is 1: 1 to 1: 3, and they are separately and simultaneously, continuously or semi-continuously charged into the reaction tank, and the reaction tank is continuously 2,000 to 20,000 rpm.
The mixture is stirred at a high speed at a rotation speed of m, and the neutralized product generated in the reaction is continuously or semi-continuously taken out of the reaction tank, then filtered, washed, dried, calcined, and then surface-treated with silicone oil or fatty acid. A method for producing coated ultrafine zinc oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27218696A JP3496858B2 (en) | 1996-10-15 | 1996-10-15 | Method for producing ultrafine zinc oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27218696A JP3496858B2 (en) | 1996-10-15 | 1996-10-15 | Method for producing ultrafine zinc oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10120418A true JPH10120418A (en) | 1998-05-12 |
| JP3496858B2 JP3496858B2 (en) | 2004-02-16 |
Family
ID=17510292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27218696A Expired - Lifetime JP3496858B2 (en) | 1996-10-15 | 1996-10-15 | Method for producing ultrafine zinc oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3496858B2 (en) |
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| WO2000069776A1 (en) * | 1999-05-12 | 2000-11-23 | Sakai Chemical Industry Co., Ltd. | Zinc oxide particles having suppressed surface activity and production and use thereof |
| JP2001199822A (en) * | 2000-01-14 | 2001-07-24 | Shiseido Co Ltd | Antibacterial mildewproofing agent and antibacterial mildewproofing composition |
| JP2007161539A (en) * | 2005-12-14 | 2007-06-28 | Sumitomo Metal Mining Co Ltd | Method for producing zinc oxide fine particle for ultraviolet shielding, and liquid dispersion for forming ultraviolet shielding agent using the fine particle and ultraviolet shielding agent |
| JP2007182382A (en) * | 1997-11-18 | 2007-07-19 | Shiseido Co Ltd | Method for producing ultraviolet-screening zinc oxide excellent in transparency |
| JP2008074911A (en) * | 2006-09-20 | 2008-04-03 | Pola Chem Ind Inc | Fine particle powder and method for producing the same |
| JP2008230915A (en) * | 2007-03-20 | 2008-10-02 | Mitsui Mining & Smelting Co Ltd | Electrically conductive zinc oxide particle and method for manufacturing the same |
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| WO2017130632A1 (en) * | 2016-01-29 | 2017-08-03 | 住友大阪セメント株式会社 | Surface-treated zinc oxide particles, dispersion liquid, cosmetic, and zinc oxide particles |
| JP2017137227A (en) * | 2016-01-29 | 2017-08-10 | 住友大阪セメント株式会社 | Surface-treated zinc oxide particle, dispersion liquid, cosmetic and zinc oxide particle |
| JP2019026525A (en) * | 2017-08-01 | 2019-02-21 | 住友大阪セメント株式会社 | Method for producing surface-treated zinc oxide particles |
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1996
- 1996-10-15 JP JP27218696A patent/JP3496858B2/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007182382A (en) * | 1997-11-18 | 2007-07-19 | Shiseido Co Ltd | Method for producing ultraviolet-screening zinc oxide excellent in transparency |
| WO2000069776A1 (en) * | 1999-05-12 | 2000-11-23 | Sakai Chemical Industry Co., Ltd. | Zinc oxide particles having suppressed surface activity and production and use thereof |
| EP1112964A1 (en) * | 1999-05-12 | 2001-07-04 | Sakai Chemical Industrial Company Ltd. | Zinc oxide particles having suppressed surface activity and production and use thereof |
| US6660380B1 (en) | 1999-05-12 | 2003-12-09 | Sakai Chemical Industry Co., Ltd. | Zinc oxide particles having suppressed surface activity and production and use thereof |
| EP1112964A4 (en) * | 1999-05-12 | 2008-01-23 | Sakai Chemical Industry Co | Zinc oxide particles having suppressed surface activity and production and use thereof |
| JP2001199822A (en) * | 2000-01-14 | 2001-07-24 | Shiseido Co Ltd | Antibacterial mildewproofing agent and antibacterial mildewproofing composition |
| JP2007161539A (en) * | 2005-12-14 | 2007-06-28 | Sumitomo Metal Mining Co Ltd | Method for producing zinc oxide fine particle for ultraviolet shielding, and liquid dispersion for forming ultraviolet shielding agent using the fine particle and ultraviolet shielding agent |
| JP2008074911A (en) * | 2006-09-20 | 2008-04-03 | Pola Chem Ind Inc | Fine particle powder and method for producing the same |
| JP2008230915A (en) * | 2007-03-20 | 2008-10-02 | Mitsui Mining & Smelting Co Ltd | Electrically conductive zinc oxide particle and method for manufacturing the same |
| EP2113528A2 (en) | 2008-04-30 | 2009-11-04 | Sumitomo Metal Mining Co., Ltd. | Ultraviolet-shielding transparent resin molding and manufacturing method of the same |
| WO2017130632A1 (en) * | 2016-01-29 | 2017-08-03 | 住友大阪セメント株式会社 | Surface-treated zinc oxide particles, dispersion liquid, cosmetic, and zinc oxide particles |
| JP2017137227A (en) * | 2016-01-29 | 2017-08-10 | 住友大阪セメント株式会社 | Surface-treated zinc oxide particle, dispersion liquid, cosmetic and zinc oxide particle |
| EP3730209A1 (en) * | 2016-06-02 | 2020-10-28 | M. Technique Co., Ltd. | Oxide particles with controlled color characteristics, and coating composition or film-like composition containing said oxide particles |
| US11033960B2 (en) | 2016-06-02 | 2021-06-15 | M. Technique Co., Ltd. | Oxide particles with controlled color characteristics, and coating composition or film-like composition containing said oxide particles |
| JP2019026525A (en) * | 2017-08-01 | 2019-02-21 | 住友大阪セメント株式会社 | Method for producing surface-treated zinc oxide particles |
| JP2020158350A (en) * | 2019-03-27 | 2020-10-01 | 三井金属鉱業株式会社 | Zinc oxide particles and production method thereof |
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| Publication number | Publication date |
|---|---|
| JP3496858B2 (en) | 2004-02-16 |
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