JPH0769621A - Magnesium fluoride hydrate sol and production thereof - Google Patents
Magnesium fluoride hydrate sol and production thereofInfo
- Publication number
- JPH0769621A JPH0769621A JP21866693A JP21866693A JPH0769621A JP H0769621 A JPH0769621 A JP H0769621A JP 21866693 A JP21866693 A JP 21866693A JP 21866693 A JP21866693 A JP 21866693A JP H0769621 A JPH0769621 A JP H0769621A
- Authority
- JP
- Japan
- Prior art keywords
- magnesium fluoride
- sol
- magnesium
- fluoride hydrate
- hydrate
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、レンズ及び陰極線管や
液晶表示装置の画像表示面などの反射防止膜用コーティ
ング剤に好適に用いられるフッ化マグネシウム水和物ゾ
ルとその製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magnesium fluoride hydrate sol suitable for use as a coating agent for an antireflection film such as lenses and cathode ray tubes and image display surfaces of liquid crystal display devices, and a method for producing the same.
【０００２】[0002]
【従来の技術】一般に、レンズ及び陰極線管や液晶表示
装置の画像表示面上には太陽光や電灯光などの外光反射
を低減し、かつ光の透過を高めるために反射防止処理が
なされている。反射防止処理は真空蒸着法やコーティン
グ法により行われており、最外層には低屈折率を有する
フッ化マグネシウムやシリカなどが用いられている。特
に反射防止コーティング剤マイクロフィラーとしてフッ
化マグネシウムゾル及び微粉末が有効であることが知ら
れている。しかし、フッ化マグネシウム粒子は分散性が
悪く、一次粒子径を著しく小さくしないと目的とする透
明性が得られない欠点を有している。また、この一次粒
子径を著しく小さくするため、生産性が悪くなる。2. Description of the Related Art Generally, a lens, a cathode ray tube, and an image display surface of a liquid crystal display device are subjected to an antireflection treatment to reduce reflection of external light such as sunlight and electric light and to enhance light transmission. There is. The antireflection treatment is performed by a vacuum deposition method or a coating method, and magnesium fluoride, silica, or the like having a low refractive index is used for the outermost layer. In particular, magnesium fluoride sol and fine powder are known to be effective as microfillers for antireflection coating agents. However, magnesium fluoride particles have poor dispersibility and have a drawback that the desired transparency cannot be obtained unless the primary particle size is remarkably reduced. Further, since the primary particle size is made extremely small, the productivity is deteriorated.
【０００３】フッ化マグネシウムゾル及び微粉末の製造
法については下記のようなものが報告されている。特開
昭６３−１２４３３２号公報には、酢酸マグネシウムと
ポリビニルアルコールの混合水溶液にフッ化水素酸水溶
液を添加し、酸性のフッ化マグネシウムのコロイド粒子
の分散液を製造する方法が提案されている。この方法で
得られるコロイド粒子の分散液は、ｐＨ２で、濃度が５
％以上では調製後直ちにゲル化する欠点を有している。The following methods have been reported for the production method of magnesium fluoride sol and fine powder. Japanese Unexamined Patent Publication No. 63-124332 proposes a method of producing a dispersion of acidic magnesium fluoride colloidal particles by adding a hydrofluoric acid aqueous solution to a mixed aqueous solution of magnesium acetate and polyvinyl alcohol. The dispersion of colloidal particles obtained by this method has a pH of 2 and a concentration of 5
If it is more than 100%, there is a drawback that gelation occurs immediately after preparation.
【０００４】特開昭６４−４１１４９号公報には、粒子
径が１００〜２００オングストロームのフッ化マグネシ
ウムの微粒子から成るゾル液を陰極線管のスクリーンパ
ネルに塗布する方法により反射防止する方法が提案され
ている。しかし、このゾル液の製造方法については記載
されていない。特開平２−２６８２４号公報には、光透
過率が５０％以上の水性及びオルガノフッ化マグネシウ
ムゾル、及びこのゾルを基体表面に塗布乾燥してなる被
膜形成体、そして、マグネシウム塩水溶液とフッ化物水
溶液とを同時添加法で反応させてゲル状沈澱物を生成さ
せ、得られた反応液を加熱熟成した後、液中の電解質を
除去する事を特徴とする水性フッ化マグネシウムゾルの
製造法が提案されている。この方法で得られたフッ化マ
グネシウムのコロイド粒子は１００〜１２０オングスト
ロームと著しく小さい粒子径を示している。しかし、塩
化マグネシウム水溶液にフッ化カリウム水溶液を添加す
る方法で得られたゾルは、コロイド粒子が１００〜３０
０オングストロームで乳白色不透明で透過率も２０％以
下であることが報告されている。Japanese Unexamined Patent Publication (Kokai) No. 64-41149 proposes a method for preventing reflection by applying a sol solution composed of fine particles of magnesium fluoride having a particle size of 100 to 200 angstroms to a screen panel of a cathode ray tube. There is. However, there is no description about a method for producing this sol solution. Japanese Unexamined Patent Publication (Kokai) No. 2-26824 discloses an aqueous or organomagnesium fluoride sol having a light transmittance of 50% or more, a film-forming body obtained by coating and drying the sol on a substrate surface, and an aqueous magnesium salt solution and an aqueous fluoride solution. A method for producing an aqueous magnesium fluoride sol is proposed which comprises reacting and with a simultaneous addition method to form a gel-like precipitate, aging the resulting reaction solution by heating, and then removing the electrolyte in the solution. Has been done. The magnesium fluoride colloidal particles obtained by this method exhibit a remarkably small particle size of 100 to 120 angstroms. However, the sol obtained by adding an aqueous solution of potassium fluoride to an aqueous solution of magnesium chloride has colloidal particles of 100 to 30.
It has been reported that it has a milky white opacity at 0 Å and a transmittance of 20% or less.
【０００５】上記方法により得られたフッ化マグネシウ
ムゾル中のフッ化マグネシウムのコロイド粒子は、いず
れもフッ化マグネシウムの無水塩であり、フッ化マグネ
シウムの水和物に関する記載はない。一方、フッ化マグ
ネシウム水和物の存在については、無機化学の古典であ
るＭｅｌｌｏｒの「Ａ Ｃｏｍｐｒｅｈｅｎｓｉｖｅ
Ｔｒｅａｔｉｓｅ ｏｎ Ｉｎｏｒｇａｎｉｃ ａｎｄ
Ｔｈｅｏｒｅｔｉｃａｌ Ｃｈｅｍｉｓｔｒｙ」や、
「Ｇｍｅｌｉｎｓ Ｈａｎｄｂｕｃｈ ｄｅｒ Ａｎｏ
ｒｇａｎｉｓｈｅｎＣｈｅｍｉｅ」にも報告が見られな
い。また、フッ化マグネシウム水和物ゾルについて記載
されている文献もない。The magnesium fluoride colloidal particles in the magnesium fluoride sol obtained by the above method are all anhydrous magnesium fluoride salts, and there is no description of magnesium fluoride hydrate. On the other hand, regarding the existence of magnesium fluoride hydrate, Mellor's “A Comprehensive”, which is a classic of inorganic chemistry, is used.
Treatise on Inorganic and
"Theoretical Chemistry",
"Gmelins Handbuch der Ano
There is no report on "rganishen Chemie". Further, there is no document describing a magnesium fluoride hydrate sol.
【０００６】[0006]
【発明が解決しようとする課題】上記フッ化マグネシウ
ムの無水塩のコロイド粒子は、それ自体結合力が小さい
ため、反射防止コーティング剤として使用する場合に
は、有機または無機のバインダーが必要となる。この場
合一次粒子径が小さいと多量のバインダーが必要とな
り、目的とする屈折率が得られなくなる欠点を有してい
る。Since the above-mentioned colloidal particles of anhydrous magnesium fluoride have a small binding force by themselves, an organic or inorganic binder is required when used as an antireflection coating agent. In this case, if the primary particle size is small, a large amount of binder is required, and the target refractive index cannot be obtained.
【０００７】上記フッ化マグネシウムの無水塩よりも屈
折率の低いフッ化物ゾル、及びそのゾルを容易に製造す
る方法が望まれている。本発明は外光反射を低減した
り、光の透過率を高めるための反射防止膜に用いられる
新規なフッ化マグネシウム水和物ゾル、及びそのゾルを
容易に製造する方法を提供することを目的とする。There is a demand for a fluoride sol having a refractive index lower than that of the anhydrous magnesium fluoride salt and a method for easily producing the sol. It is an object of the present invention to provide a novel magnesium fluoride hydrate sol used for an antireflection film for reducing external light reflection or increasing light transmittance, and a method for easily producing the sol. And
【０００８】[0008]
【課題を解決するための手段】本発明は、ＭｇＦ2 ・ｎ
Ｈ2 Ｏ（但し、ｎは０．２５〜０．５）の組成を有し、
一次粒子径が１０〜１００ｎｍであるフッ化マグネシウ
ム水和物のコロイド粒子からなるゾルである。本発明の
フッ化マグネシウム水和物ゾルは、フッ化マグネシウム
水和物のコロイド粒子が、水及び／又は有機溶媒に分散
したゾルである。SUMMARY OF THE INVENTION The present invention is directed to MgF 2 .n
Has a composition of H 2 O (where n is 0.25 to 0.5),
It is a sol composed of colloidal particles of magnesium fluoride hydrate having a primary particle diameter of 10 to 100 nm. The magnesium fluoride hydrate sol of the present invention is a sol in which magnesium fluoride hydrate colloidal particles are dispersed in water and / or an organic solvent.
【０００９】本発明のフッ化マグネシウム水和物水性ゾ
ルの製造方法は、（ａ）；マグネシウム塩水溶液にフッ
化物水溶液を、１．９〜２．０のＦ／Ｍｇモル比となる
様に添加し、フッ化マグネシウム水和物のコロイド粒子
の凝集体スラリーを生成させる工程、（ｂ）；（ａ）工
程により得られたフッ化マグネシウム水和物のコロイド
粒子の凝集体スラリー中の副生塩類を除去する工程、よ
りなる。The method for producing a magnesium fluoride hydrate aqueous sol of the present invention comprises (a); adding an aqueous fluoride solution to an aqueous magnesium salt solution so that the F / Mg molar ratio is 1.9 to 2.0. And (b); a by-product salt in the aggregate slurry of magnesium fluoride hydrate colloidal particles obtained by the step (b); And a step of removing.
【００１０】本発明に使用されるマグネシウム塩は、水
に可溶の塩であり、例えば、塩化マグネシウム、硝酸マ
グネシウム、硫酸マグネシウム、スルファミン酸マグネ
シウム、酢酸マグネシウム、ギ酸マグネシウム等が挙げ
られ、単独または２種以上混合して使用することができ
る。本発明に使用されるフッ化物は、水に可溶の塩であ
り、例えば、フッ化ナトリウム、フッ化カリウム、フッ
化セシウム、フッ化ルビジウム、フッ化アンモニウム、
フッ化グアニジン、フッ化第４級アンモニウム、酸性フ
ッ化アンモニウム、フッ化水素が挙げられ、単独または
２種以上混合して使用することが出来る。The magnesium salt used in the present invention is a water-soluble salt, and examples thereof include magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium sulfamate, magnesium acetate, magnesium formate, etc., either alone or in the form of 2 A mixture of two or more species can be used. The fluoride used in the present invention is a water-soluble salt, for example, sodium fluoride, potassium fluoride, cesium fluoride, rubidium fluoride, ammonium fluoride,
Examples thereof include guanidine fluoride, quaternary ammonium fluoride, ammonium acid fluoride and hydrogen fluoride, which may be used alone or in combination of two or more.
【００１１】本発明のフッ化マグネシウム水和物ゾルの
製造法において、マグネシウム塩水溶液とフッ化物水溶
液の混合は、マグネシウム塩水溶液にフッ化物水溶液
を、フッ素とマグネシウムの比がＦ／Ｍｇモル比で１．
９〜２．０になるように添加することが重要である。マ
グネシウム塩水溶液とフッ化物水溶液を、そのマグネシ
ウム塩とフッ化物の量が、フッ化マグネシウムを生成す
る化学量論量を常に維持する様にしながら同時添加する
方法、又は、フッ化物水溶液にマグネシウム塩水溶液を
添加する方法では、目的とするフッ化マグネシウム水和
物ゾルを、効率よく製造することが出来ない。In the method for producing a magnesium fluoride hydrate sol of the present invention, the magnesium salt aqueous solution and the fluoride aqueous solution are mixed by mixing the magnesium salt aqueous solution with the fluoride aqueous solution at a fluorine / magnesium ratio of F / Mg molar ratio. 1.
It is important to add 9 to 2.0. A method of simultaneously adding an aqueous solution of magnesium salt and an aqueous solution of fluoride while keeping the amounts of the magnesium salt and fluoride to maintain a stoichiometric amount for producing magnesium fluoride, or an aqueous solution of magnesium salt in the aqueous fluoride solution. With the method of adding, the target magnesium fluoride hydrate sol cannot be efficiently produced.
【００１２】本発明の（ａ）工程でのマグネシウム塩水
溶液へのフッ化物水溶液の添加並びに混合は、サタケ式
撹拌機、ファウドラー型撹拌機、ディスパー、ホモジナ
イザー等の装置を用い、０〜１００℃の温度で行われ、
撹拌下、この添加に要する時間は０．１〜１０時間で行
うことが出来る。（ａ）工程で生成するフッ化マグネシ
ウム水和物の濃度は、ＭｇＦ2 として０．１〜１０重量
％になるように調製することが好ましい。The addition and mixing of the fluoride aqueous solution to the magnesium salt aqueous solution in the step (a) of the present invention is carried out at 0 to 100 ° C. by using a device such as a Satake type stirrer, a Faudler type stirrer, a disper, a homogenizer and the like. Done at temperature,
The time required for this addition under stirring can be 0.1 to 10 hours. It is preferable to adjust the concentration of the magnesium fluoride hydrate produced in the step (a) to be 0.1 to 10% by weight as MgF 2 .
【００１３】（ａ）工程により一次粒子径が１０〜１０
０ｎｍのフッ化マグネシウム水和物のコロイド粒子の凝
集体が生成し、スラリーとなる。このスラリーは静定に
よりフッ化マグネシウム水和物のコロイド粒子の凝集体
が沈降分離する。この凝集体の生成は、（ａ）工程によ
り副生する塩類、それはマグネシウム塩とフッ化物、即
ち、マグネシウムイオンとフッ素イオンのそれぞれのカ
ウンターイオンにより形成される塩類の濃度が高いこと
に起因している。According to the step (a), the primary particle size is 10 to 10
Aggregates of colloidal particles of 0 nm magnesium fluoride hydrate are formed to form a slurry. Aggregates of colloidal particles of magnesium fluoride hydrate are settled and separated by static determination in this slurry. The formation of this aggregate is due to the high concentration of the salts by-produced in the step (a), that is, the salts formed by the magnesium salt and the fluoride, that is, the counter ions of magnesium ion and fluorine ion. There is.
【００１４】本発明における（ｂ）工程は、（ａ）工程
により得られたフッ化マグネシウム水和物のコロイド粒
子の凝集体スラリーから副生塩類を除去する工程であ
る。副生塩類を除去する方法としては、限外ろ過膜、逆
浸透膜などによる膜ろ過洗浄法、イオン交換法、静定分
離法などを利用することが出来るが、限外ろ過膜を用い
た膜ろ過洗浄法が最も好ましい。また、必要に応じて膜
ろ過洗浄法と他の方法を併用することが出来る。特にチ
ューブ式限外ろ過膜を用いることにより効果的に副生塩
類を除去することが可能である。限外ろ過は、膜の材質
にもよるが、通常０〜８０℃で行われ、充分に塩類を除
去するために連続叉は断続的に注水しながら行う必要が
ある。ろ過時間は特に限定されないが、通常１〜５０時
間で行われる。The step (b) in the present invention is a step of removing by-product salts from the aggregate slurry of the magnesium fluoride hydrate colloidal particles obtained in the step (a). As a method for removing by-product salts, an ultrafiltration membrane, a membrane filtration washing method using a reverse osmosis membrane, an ion exchange method, a static separation method, etc. can be used, but a membrane using an ultrafiltration membrane is used. The filtration washing method is the most preferable. If necessary, the membrane filtration washing method can be used in combination with other methods. In particular, by-product salts can be effectively removed by using a tube type ultrafiltration membrane. Ultrafiltration is usually carried out at 0 to 80 ° C., though it depends on the material of the membrane, and it is necessary to carry out continuous or intermittent water injection in order to sufficiently remove salts. The filtration time is not particularly limited, but is usually 1 to 50 hours.
【００１５】限外ろ過により副生塩類を除去することに
より、フッ化マグネシウム水和物のコロイド粒子の凝集
体は小さくなり、フッ化マグネシウム水和物水性ゾルを
得ることが出来る。（ｂ）工程で得られたフッ化マグネ
シウム水和物水性ゾルは、電子顕微鏡による観察で、一
次粒子径が１０〜１００ｎｍである。限外ろ過の後、さ
らに、陽、陰イオン交換を行うことにより透明性の良好
な水性ゾルを得ることが出来る。本発明の（ｂ）工程で
得られたフッ化マグネシウム水和物水性ゾルは、フッ化
マグネシウム水和物の濃度が２〜２０重量％である。本
発明の（ｂ）工程により得られたフッ化マグネシウム水
和物水性ゾルは、ＭｇＦ2 として５重量％での光透過率
が５０以下である。この光透過率は、厚さ１ｃｍの水に
おける波長５００ｎｍの光の透過率を１００とし、厚さ
１ｃｍのフッ化マグネシウム水和物ゾルにおける同波長
光の透過率の相対値を示したものである。By removing the by-product salts by ultrafiltration, the agglomerates of colloidal particles of magnesium fluoride hydrate are reduced, and a magnesium fluoride hydrate aqueous sol can be obtained. The magnesium fluoride hydrate aqueous sol obtained in the step (b) has a primary particle diameter of 10 to 100 nm as observed by an electron microscope. After ultrafiltration, cation and anion exchange is further carried out to obtain an aqueous sol having good transparency. The magnesium fluoride hydrate aqueous sol obtained in the step (b) of the present invention has a magnesium fluoride hydrate concentration of 2 to 20% by weight. The magnesium fluoride hydrate aqueous sol obtained by the step (b) of the present invention has a light transmittance of 50 or less at 5% by weight as MgF 2 . The light transmittance is a relative value of the transmittance of light of the same wavelength in a magnesium fluoride hydrate sol having a thickness of 1 cm, where the transmittance of light having a wavelength of 500 nm in water having a thickness of 1 cm is 100. .
【００１６】本発明において（ｃ）工程でフッ化マグネ
シウム水和物水性ゾルの水を、常法により、減圧または
常圧で有機溶媒に置換することによりオルガノゾルを得
ることが出来る。本発明において有機溶媒としてはメタ
ノール、エタノール、イソプロパノール、ｎ−プロパノ
ール、ＤＭＦ、ＤＭＡＣ、エチレングリコール、プロピ
ルセロソルブなどが挙げられ、単独又は２種以上混合し
て使用する事ができる。In the present invention, an organosol can be obtained by substituting water of the magnesium fluoride hydrate aqueous sol with an organic solvent under reduced pressure or atmospheric pressure by a conventional method in the step (c). In the present invention, examples of the organic solvent include methanol, ethanol, isopropanol, n-propanol, DMF, DMAC, ethylene glycol, and propyl cellosolve, which can be used alone or in combination of two or more.
【００１７】（ｃ）工程で得られるフッ化マグネシウム
水和物オルガノゾルは、フッ化マグネシウム水和物の濃
度が２〜２０重量％濃度であり、電子顕微鏡による観察
で一次粒子径は、１０〜１００ｎｍである。また、光透
過率は、上記方法で測定して５０以上である。本発明の
方法により得られたフッ化マグネシウム水和物ゾルは、
そのゾルを１１０℃で乾燥し粉末としてＸ線回折を行っ
たところ、その測定結果は、ＡＳＴＭ（Ｉｎｄｅｘ ｔ
ｏ ｔｈｅ Ｘ−ｒａｙ Ｐｏｗｄｅｒ Ｄａｔｅ Ｆ
ｉｌｅＩｎｏｒｇａｎｉｃ）に記載されているフッ化マ
グネシウムＸ線回折パターンＮｏ．６−０２９０とＸ線
回折ピークが一致せず、メインピークのシフト及び新た
な小さなピークの存在が確認された。The magnesium fluoride hydrate organosol obtained in the step (c) has a magnesium fluoride hydrate concentration of 2 to 20% by weight and a primary particle diameter of 10 to 100 nm as observed by an electron microscope. Is. The light transmittance is 50 or more as measured by the above method. Magnesium fluoride hydrate sol obtained by the method of the present invention,
When the sol was dried at 110 ° C. and subjected to X-ray diffraction as a powder, the measurement result was ASTM (Index text).
o the X-ray Powder Date F
magnesium Inorganic) magnesium fluoride X-ray diffraction pattern No. The X-ray diffraction peaks did not coincide with those of 6-0290, and the shift of the main peak and the presence of a new small peak were confirmed.
【００１８】一方、本発明の方法により得られたフッ化
マグネシウム水和物ゾルは、そのゾルを１１０℃で乾燥
し粉末として示差熱分析（ＤＴＡ−ＴＧ分析）を行った
ところ、その測定結果は、１４０〜１９０℃に吸熱ピー
クが認められ、６．５〜１３重量％の重量減が測定され
た。また、カールフィッシャー法により、この重量減は
水であることを確認した。On the other hand, the magnesium fluoride hydrate sol obtained by the method of the present invention was dried at 110 ° C. and subjected to differential thermal analysis (DTA-TG analysis) as a powder. , An endothermic peak was observed at 140 to 190 ° C., and a weight loss of 6.5 to 13% by weight was measured. Moreover, it was confirmed by Karl Fischer's method that this weight loss was water.
【００１９】以上の結果から本発明のフッ化マグネシウ
ム水和物ゾル乾燥物は、明らかに結晶水を有しており、
その組成は、ＭｇＦ2 ・ｎＨ2 Ｏにおいて、ｎは０．２
５〜０．５に相当する。この結晶水は（ａ）工程の反応
温度が高くなるほど減少する傾向を示している。上記示
差熱分析の結果、脱水は４００〜５００℃で終了する。
５００℃焼成物のＸ線回折の結果は、上記ＡＳＴＭ Ｎ
ｏ．６−０２９０のフッ化マグネシウムのＸ線回折ピー
クと完全に一致し、他のピークの存在は認められなかっ
た。From the above results, the dried magnesium fluoride hydrate sol of the present invention clearly has water of crystallization,
Its composition is MgF 2 · nH 2 O, where n is 0.2.
It corresponds to 5 to 0.5. This water of crystallization tends to decrease as the reaction temperature in step (a) increases. As a result of the differential thermal analysis, dehydration ends at 400 to 500 ° C.
The result of X-ray diffraction of the 500 ° C. calcined product is
o. It completely coincided with the X-ray diffraction peak of magnesium fluoride of 6-0290, and the presence of other peaks was not recognized.
【００２０】さらに、本発明の方法により得られたフッ
化マグネシウム水和物ゾルは、そのゾルを１１０℃で乾
燥し粉末として湿式分析（ＩＣＰ分析及びイオンクロマ
トグラフィー分析）を行ったところ、その測定結果は、
フッ素とマグネシウムの比は、Ｆ／Ｍｇのモル比が２．
０であった。以上の結果から、本発明の方法により得ら
れたフッ化マグネシウム水和物は、ＭｇＦ2 ・ｎＨ2 Ｏ
（但し、ｎは０．２５〜０．５）である事が判明した。Further, the magnesium fluoride hydrate sol obtained by the method of the present invention was dried at 110 ° C. and subjected to wet analysis (ICP analysis and ion chromatography analysis) as a powder. Result is,
Regarding the ratio of fluorine to magnesium, the molar ratio of F / Mg is 2.
It was 0. From the above results, the magnesium fluoride hydrate obtained by the method of the present invention is MgF 2 · nH 2 O
(However, n was 0.25 to 0.5).
【００２１】[0021]
【作用】本発明の（ａ）工程において、マグネシウム塩
水溶液とフッ化物水溶液の反応は、フッ素とマグネシウ
ムの比がＦ／Ｍｇモル比で１．９〜２．０であり、１．
９未満でもよいが、未反応のＭｇＣｌ2 が多くなるため
効率的ではなくなる。また、２．０以上では（ａ）工程
の反応の生成物はゲル状となり、（ｂ）工程での塩類除
去時に、スラリーの粘度が高くなり、生産性が著しく低
下するので好ましくない。この理由は明かではないが、
本発明の方法では、まずＭｇ（ＯＨ）x Ｆ y ・ｚＨ2 Ｏ
（ｘ＞０、ｙ＜２）の塩基性フッ化マグネシウムが生成
し、最終的に限りなくＭｇＦ2 ・ｚＨ2 Ｏに近くなるた
めと推定される。In the step (a) of the present invention, magnesium salt
The reaction between an aqueous solution and an aqueous solution of fluoride is
The F / Mg molar ratio is 1.9 to 2.0.
It may be less than 9, but unreacted MgCl2Because there are many
It becomes less efficient. If it is 2.0 or more, the step (a) is performed.
The product of the reaction of step 2 becomes a gel, and salt removal in step (b)
When leaving, the viscosity of the slurry becomes high and the productivity is extremely low.
It is not preferable because it will be lowered. The reason for this is not clear,
In the method of the present invention, first, Mg (OH)xF y・ ZH2O
(X> 0, y <2) basic magnesium fluoride is generated
And finally MgF2・ ZH2It ’s closer to O
Presumed to be
【００２２】（ａ）工程の温度は０〜１００℃で、１０
０℃以上では脱水が進むため好ましくない。（ａ）工程
の時間は０．１〜１０時間であり、０．１時間未満でも
良いが混合が不充分になるため好ましくない。また、１
０時間を越えても良いが、製造時間が必要以上に長くな
り好ましくない。The temperature of the step (a) is 0 to 100 ° C. and is 10
Dehydration proceeds at 0 ° C or higher, which is not preferable. The time of the step (a) is 0.1 to 10 hours and may be less than 0.1 hours, but it is not preferable because the mixing becomes insufficient. Also, 1
It may be longer than 0 hours, but it is not preferable because the production time becomes longer than necessary.
【００２３】（ａ）工程のフッ化マグネシウム水和物の
濃度は、ＭｇＦ2 として０．１〜１０重量％であり、
０．１重量％未満でも良いが効率的ではなく、また、１
０重量％を越える濃度でも良いが液の粘度が高くなり反
応が不均一になるため好ましくない。０．５〜２．０重
量％が最も好ましい。（ｂ）工程の温度は０〜８０℃で
あり、温度が高い方がろ過速度が大きくなるので有効で
あるが、ろ過温度が高くなると脱水が進むことから室温
〜６０℃がより好ましい。The concentration of the magnesium fluoride hydrate in step (a) is 0.1 to 10% by weight as MgF 2 ,
It may be less than 0.1% by weight, but it is not efficient, and 1
A concentration of more than 0% by weight is acceptable, but it is not preferable because the viscosity of the liquid increases and the reaction becomes nonuniform. Most preferred is 0.5 to 2.0% by weight. The temperature in the step (b) is 0 to 80 ° C., and the higher the temperature, the more effective is the filtration rate. However, the higher the filtration temperature is, the more preferable the temperature is from room temperature to 60 ° C. because dehydration proceeds.
【００２４】（ｂ）工程の時間は１〜５０時間で、５０
時間以上でも良いが製造時間が必要以上に長くなり好ま
しくない。（ｃ）工程の溶媒置換温度は溶媒の沸点によ
り異なるが、置換時フッ化マグネシウム水和物の脱水が
起こらないように減圧で出来るだけ低温で行うのが好ま
しい。The time of the step (b) is 1 to 50 hours, and is 50
It may be longer than that, but it is not preferable because the manufacturing time becomes longer than necessary. Although the solvent replacement temperature in the step (c) varies depending on the boiling point of the solvent, it is preferably carried out under reduced pressure as low as possible so that dehydration of the magnesium fluoride hydrate does not occur during the replacement.
【００２５】（ｂ）または（ｃ）工程で得られるフッ化
マグネシウム水和物水性ゾルまたはオルガノゾルの濃度
はいずれも２〜２０重量％であり、２重量％未満でも良
いが、使用時バインダーと混合使用されることにより更
に薄くなるため好ましくない。また、２０重量％以上で
も良いが、この場合にはゾルの粘度が高くなり扱いにく
くなるため好ましくない。The concentration of the magnesium fluoride hydrate aqueous sol or organosol obtained in step (b) or (c) is 2 to 20% by weight, and may be less than 2% by weight, but it is mixed with the binder at the time of use. It is not preferable because it becomes thinner when used. Further, it may be 20% by weight or more, but in this case, the viscosity of the sol becomes high and it becomes difficult to handle, which is not preferable.
【００２６】本発明においてフッ化マグネシウム水和物
のコロイド粒子の一次粒子径は、電子顕微鏡による観察
で１０〜１００ｎｍであり、また、１００ｎｍ以上では
反射防止膜として効果的な厚みである１００ｎｍを越え
るため好ましくない。また、（ａ）工程の反応温度が高
いほど、このフッ化マグネシウム水和物のコロイド粒子
の一次粒子径は大きくなる傾向を示す。In the present invention, the primary particle size of colloidal particles of magnesium fluoride hydrate is 10 to 100 nm as observed by an electron microscope, and when it is 100 nm or more, it exceeds 100 nm which is an effective thickness as an antireflection film. Therefore, it is not preferable. Further, the higher the reaction temperature in step (a), the larger the primary particle size of the colloidal particles of magnesium fluoride hydrate tends to be.
【００２７】本発明において、フッ化マグネシウム水和
物は、フッ化マグネシウムの無水塩よりも屈折率が低
く、このフッ化マグネシウム水和物のゾルを用いる事に
より、良好な反射防止効果を発現する事が出来る。In the present invention, magnesium fluoride hydrate has a lower refractive index than the anhydrous magnesium fluoride salt, and by using this magnesium fluoride hydrate sol, a good antireflection effect is exhibited. I can do things.
【００２８】[0028]
実施例１ （ａ）工程 塩化マグネシウム（ＭｇＣｌ2 ・６Ｈ2 Ｏ、試薬特級、
小宗化学製）２４３６ｇ（ＭｇＣｌ2 として１１２５
ｇ）を、純水４０ｋｇに溶解して塩化マグネシウム水溶
液４２．４ｋｇを調製した。この水溶液中のＭｇＣｌ2
濃度は２．６５重量％であった。Example 1 Step (a) Magnesium chloride (MgCl 2 .6H 2 O, reagent grade,
2436 g (manufactured by Komune Kagaku) (1125 as MgCl 2
g) was dissolved in 40 kg of pure water to prepare 42.4 kg of an aqueous magnesium chloride solution. MgCl 2 in this aqueous solution
The concentration was 2.65% by weight.
【００２９】一方、酸性フッ化アンモニウム（ＮＨ4 Ｆ
・ＨＦ、試薬特級、森田化学製）６８５ｇを、純水４０
ｋｇに溶解した後、２８％アンモニア水（試薬、小宗化
学製）７３０ｇを添加し、フッ化アンモニウム水溶液４
１．４ｋｇ（ＮＨ4 Ｆとして８６７ｇ）を調製した。こ
の水溶液中のＮＨ4 Ｆ濃度は２．０９重量％であった。On the other hand, acidic ammonium fluoride (NH 4 F
・ HF, reagent special grade, Morita Chemical Co., Ltd.) 685 g, pure water 40
After dissolving in kg, 730 g of 28% ammonia water (reagent, manufactured by Kosou Kagaku) was added, and ammonium fluoride aqueous solution 4 was added.
1.4 kg (867 g as NH 4 F) was prepared. The NH 4 F concentration in this aqueous solution was 2.09% by weight.
【００３０】上記の塩化マグネシウム水溶液を、２００
リットルの容器に仕込み、ディスパーにて強く撹拌しな
がら、室温で上記フッ化アンモニウム水溶液を３０分間
で添加した後、更に１時間撹拌を続行し、フッ化マグネ
シウム水和物のコロイド粒子のスラリーを８３．８ｋｇ
得た。上記塩化マグネシウムとフッ化アンモニウムのフ
ッ素とマグネシウムの比は、Ｆ／Ｍｇモル比で１．９８
であった。得られたフッ化マグネシウム水和物のコロイ
ド粒子のスラリーは、ゾルに近いコロイド色を示すが静
定により沈降分離する傾向を示し、このフッ化マグネシ
ウム水和物のコロイド粒子は凝集体を形成している。こ
のスラリーはｐＨ７．０７、電導度４０ｍｓ／ｃｍで、
フッ化マグネシウム水和物の濃度はＭｇＦ2 として０．
８７重量％であった。副生する塩は塩化アンモニウムで
あり、スラリー中に１．５１重量％であった。The above magnesium chloride aqueous solution was added to 200
In a liter container, the above ammonium fluoride aqueous solution was added for 30 minutes at room temperature while stirring vigorously with a disper, and the stirring was continued for another 1 hour to obtain a slurry of magnesium fluoride hydrate colloidal particles of 83 .8 kg
Obtained. The ratio of fluorine to magnesium in the above-mentioned magnesium chloride and ammonium fluoride is 1.98 in terms of F / Mg molar ratio.
Met. The obtained magnesium fluoride hydrate colloidal particle slurry shows a colloidal color close to that of a sol, but tends to settle and separate by static determination, and the magnesium fluoride hydrate colloidal particles form aggregates. ing. This slurry has a pH of 7.07, an electric conductivity of 40 ms / cm,
The concentration of magnesium fluoride hydrate was 0.1 as MgF 2 .
It was 87% by weight. The by-product salt was ammonium chloride, which was 1.51% by weight in the slurry.
【００３１】（ｂ）工程 （ａ）工程で得られたフッ化マグネシウム水和物のコロ
イド粒子のスラリー８３．８ｋｇを、チューブ式限外ろ
過装置〔ＵＦ（ＰＳ−１５０）、三菱レイヨンエンジニ
アリング（株）製〕を用いて純水２７０ｋｇを限外ろ過
速度と同じ速度で添加しながら、ろ過洗浄を行った。液
温は２５℃でろ過洗浄時間は１８．５時間であった。ろ
過洗浄時の濃度はＭｇＦ2 として２．５重量％で、ろ
過、洗浄後限外ろ過装置により濃縮を行い、フッ化マグ
ネシウム水和物水性ゾル（Ｉ）１２．７４ｋｇを得た。
沈降物は認められず、ゾル化率は１００％であった。Step (b) 83.8 kg of a slurry of magnesium fluoride hydrate colloidal particles obtained in the step (a) was added to a tube type ultrafiltration device [UF (PS-150), Mitsubishi Rayon Engineering Co., Ltd.]. )) Was added while 270 kg of pure water was added at the same rate as the ultrafiltration rate. The liquid temperature was 25 ° C., and the filter washing time was 18.5 hours. The concentration at the time of filtration and washing was 2.5% by weight as MgF 2 , and after filtration and washing, concentration was carried out by an ultrafiltration device to obtain 12.74 kg of magnesium fluoride hydrate aqueous sol (I).
No sediment was observed, and the sol formation rate was 100%.
【００３２】得られた水性ゾル（Ｉ）は比重１．０４
２、ｐＨ７．１０、粘度１．８ｃ．ｐ．、フッ化マグネ
シウム水和物の濃度は５．９重量％、電導度３５５μｓ
／ｃｍであり、フッ化マグネシウム水和物の収率は９１
％であった。また、この水性ゾル（Ｉ）の光透過率（Ｍ
ｇＦ2 として５重量％）は２８．６％であった。電子顕
微鏡観察の結果、フッ化マグネシウム水和物のコロイド
粒子の一次粒子径は２０〜４０ｎｍで、動的光散乱法に
よる粒子径は３３６ｎｍであった。動的光散乱法による
粒子径は、市販の米国Ｃｏｕｌｔｅｒ社製Ｎ4 装置によ
り測定した。The obtained aqueous sol (I) has a specific gravity of 1.04.
2, pH 7.10, viscosity 1.8 c. p. , Magnesium fluoride hydrate concentration 5.9% by weight, conductivity 355μs
/ Cm, and the yield of magnesium fluoride hydrate is 91.
%Met. In addition, the light transmittance of this aqueous sol (I) (M
5% by weight as gF 2 ) was 28.6%. As a result of electron microscope observation, the primary particle diameter of the colloidal particles of magnesium fluoride hydrate was 20 to 40 nm, and the particle diameter measured by the dynamic light scattering method was 336 nm. The particle size by the dynamic light scattering method was measured by a commercially available N 4 apparatus manufactured by Coulter Co., USA.
【００３３】得られた水性ゾル（Ｉ）を１１０℃で乾燥
した粉末と５００℃で焼成した粉末のＸ線回折図を図
１、２に示す。５００℃焼成物は、ＡＳＴＭのＮｏ．６
−０２９０と完全に一致したが、１１０℃乾燥物はこれ
と同一ではなかった。得られた水性ゾル（Ｉ）を１１０
℃で乾燥した粉末の示差熱分析の測定結果は、１８４℃
に吸熱ピークを示し、重量減は１１．５重量％であった
（図３）。これよりフッ化マグネシウム水和物の組成
は、ＭｇＦ2 ・ｘＨ2 Ｏとするとｘ＝０．４５５とな
り、ＭｇＦ2 ・１／２Ｈ2 Ｏといえる。The X-ray diffraction patterns of the powder obtained by drying the obtained aqueous sol (I) at 110 ° C. and the powder calcined at 500 ° C. are shown in FIGS. The 500 ° C. calcined product is ASTM No. 6
Completely consistent with -0290, but the 110 ° C dry matter was not the same. The obtained aqueous sol (I) was added to 110
The measurement result of the differential thermal analysis of the powder dried at ℃ was 184 ℃.
Shows an endothermic peak and the weight loss was 11.5% by weight (FIG. 3). From this, the composition of magnesium hydrate hydrate is x = 0.455 when MgF 2 · xH 2 O is used, and it can be said that the composition is MgF 2 · 1 / 2H 2 O.
【００３４】水性ゾル（Ｉ）５００ｇに純水１５０ｇ加
え、ＭｇＦ2 濃度４重量％に希釈した後、陽イオン交換
樹脂（アンバーライトＩＲ−１２０Ｂ）を充填したカラ
ム、及び、陰イオン交換樹脂（アンバーライトＩＲＡ−
４１０）を充填したカラムに通液して得られた水性ゾル
を、ロータリーエバポレーターで濃縮して水性ゾル（Ｉ
Ｉ）１８３ｇを得た。得られた水性ゾル（ＩＩ）は比重
１．１１０、ｐＨ８．１８、粘度１９ｃ．ｐ．、フッ化
マグネシウム水和物の濃度は１６．１重量％、電導度４
３７μｓ／ｃｍであった。また、この水性ゾル（ＩＩ）
の光透過率（ＭｇＦ2 として５重量％）は３３．９％で
あった。電子顕微鏡観察の結果、フッ化マグネシウム水
和物のコロイド粒子の一次粒子径は、１０〜２０ｎｍ
で、動的光散乱粒子径は１９０ｎｍであった。After adding 150 g of pure water to 500 g of the aqueous sol (I) and diluting it to a MgF 2 concentration of 4% by weight, a column packed with a cation exchange resin (Amberlite IR-120B) and an anion exchange resin (Amber). Light IRA-
The aqueous sol obtained by passing through the column filled with 410) is concentrated by a rotary evaporator to obtain an aqueous sol (I
I) 183 g was obtained. The obtained aqueous sol (II) has a specific gravity of 1.110, a pH of 8.18 and a viscosity of 19 c. p. , Magnesium fluoride hydrate concentration is 16.1% by weight, conductivity 4
It was 37 μs / cm. Also, this aqueous sol (II)
The light transmittance (5% by weight as MgF 2 ) was 33.9%. As a result of electron microscope observation, the primary particle size of the colloidal particles of magnesium fluoride hydrate is 10 to 20 nm.
The diameter of the dynamic light scattering particles was 190 nm.
【００３５】実施例２ （ｂ）工程で得られたフッ化マグネシウム水和物水性ゾ
ル（Ｉ）（フッ化マグネシウム水和物の濃度は、５．９
重量％）７２６ｇは、（ｃ）工程として、ロータリーエ
バポレーターにて減圧下に液温２０〜４０℃でイソプロ
ピルアルコール約９リットルを連続的にチャージしなが
ら溶媒置換を行い、フッ化マグネシウム水和物イソプロ
ピルアルコールゾル４１１ｇを得た。置換時間は９．５
時間で、置換時のフッ化マグネシウム水和物濃度は１０
〜２０重量％であった。Example 2 Magnesium fluoride hydrate aqueous sol (I) obtained in step (b) (concentration of magnesium fluoride hydrate is 5.9)
(Wt%) 726 g was subjected to solvent substitution as a step (c) while continuously charging about 9 liters of isopropyl alcohol at a liquid temperature of 20 to 40 ° C. under reduced pressure with a rotary evaporator to obtain magnesium fluoride hydrate isopropyl. 411 g of alcohol sol was obtained. Replacement time is 9.5
And the concentration of magnesium fluoride hydrate at the time of substitution is 10
Was about 20% by weight.
【００３６】得られたフッ化マグネシウム水和物イソプ
ロピルアルコールゾルは比重０．８４４、水で１＋１に
希釈した時のｐＨは６．８３、粘度５．６ｃ．ｐ．、フ
ッ化マグネシウム水和物の濃度は８．９重量％、水分
０．５６重量％であった。このオルガノゾルの光透過率
（ＭｇＦ2 として５重量％）は９４．８％であった。電
子顕微鏡観察の結果、フッ化マグネシウム水和物のコロ
イド粒子の一次粒子径は水性ゾル（Ｉ）と同じで２０〜
４０ｎｍで、動的光散乱粒子径は２７４ｎｍであった。
また、得られたオルガノゾルの１１０℃で乾燥した粉末
の示差熱分析の測定結果は１７０℃に吸熱ピークを示
し、重量減は１１．５％であり、水性ゾル（Ｉ）と同じ
であった。また、このオルガノゾルの１１０℃で乾燥し
た粉末の屈折率を液浸法により測定した結果、屈折率は
１．３８５であった。The obtained magnesium fluoride hydrate isopropyl alcohol sol has a specific gravity of 0.844, a pH of 6.83 when diluted to 1 + 1 with water, and a viscosity of 5.6 c. p. The concentration of magnesium fluoride hydrate was 8.9% by weight, and the water content was 0.56% by weight. The light transmittance of this organosol (5% by weight as MgF 2 ) was 94.8%. As a result of electron microscopic observation, the primary particle size of the colloidal particles of magnesium fluoride hydrate was 20 to 20
At 40 nm, the dynamic light scattering particle size was 274 nm.
Further, the measurement result of the powder of the obtained organosol dried at 110 ° C by differential thermal analysis showed an endothermic peak at 170 ° C, and the weight loss was 11.5%, which was the same as the aqueous sol (I). The refractive index of the powder of this organosol dried at 110 ° C. was measured by the liquid immersion method, and as a result, the refractive index was 1.385.
【００３７】得られた水性ゾル（ＩＩ）及びオルガノゾ
ルはいずれも室温６ヶ月以上放置しても分離、増粘など
の異常は認められず安定であった。水性ゾル（Ｉ）は放
置により若干分離する傾向を示した。 実施例３ エチルシリケート２８（コルコート社製）２０８ｇをイ
ソプロピルアルコール６００ｇに溶解し、この溶液に撹
拌下、室温でイソプロピルアルコール３００ｇとシュウ
酸１ｇと水９０ｇからなる混合液を３０分間で添加した
後、７８℃還流下で２時間加熱し、エチルシリケート系
薄膜化剤（ＳｉＯ2 濃度５重量％）を作成した。The obtained aqueous sol (II) and organosol were both stable even after standing at room temperature for 6 months or longer without any abnormality such as separation or thickening. The aqueous sol (I) tended to separate slightly when left standing. Example 3 208 g of ethyl silicate 28 (manufactured by Colcoat) was dissolved in 600 g of isopropyl alcohol, and a mixed solution of 300 g of isopropyl alcohol, 1 g of oxalic acid and 90 g of water was added to this solution at room temperature with stirring for 30 minutes. The mixture was heated at 78 ° C. under reflux for 2 hours to prepare an ethyl silicate-based thin film forming agent (SiO 2 concentration 5% by weight).
【００３８】このエチルシリケート系薄膜化剤１６０ｇ
に（ｃ）工程で得られたフッ化マグネシウム水和物イソ
プロピルアルコールゾル（フッ化マグネシウム水和物の
濃度は８．９重量％）２５４ｇを撹拌下に添加し、反射
防止コーティング剤４１４ｇを得た。このコーティング
剤は固形分７．４％、フッ化マグネシウム水和物とエチ
ルシリケート系薄膜化剤中のＳｉＯ2 は、（フッ化マグ
ネシウム水和物）／（ＳｉＯ2 ）の重量比が２．８３で
あった。このコーティング剤をイソプロピルアルコール
で約３倍に希釈し、バーコーターにてガラス板（ソーダ
ライム）に塗布し、１１０℃３０分間乾燥を行い、反射
防止コート膜を形成させた。膜厚は約０．１μであっ
た。このガラス板の５５０ｎｍの波長での透過率を測定
した結果、未処理ガラス板は９１．６１であったのに対
して、反射防止膜コート処理をしたガラス板は９３．９
２であり、反射防止効果が認められた。160 g of this ethyl silicate thin film forming agent
254 g of magnesium fluoride hydrate isopropyl alcohol sol (concentration of magnesium fluoride hydrate is 8.9% by weight) obtained in step (c) was added to the mixture under stirring to obtain 414 g of antireflection coating agent. . This coating agent has a solid content of 7.4%, and magnesium fluoride hydrate and SiO 2 in the ethyl silicate thin film forming agent have a (magnesium fluoride hydrate) / (SiO 2 ) weight ratio of 2.83. Met. This coating agent was diluted about 3 times with isopropyl alcohol, applied on a glass plate (soda lime) with a bar coater, and dried at 110 ° C. for 30 minutes to form an antireflection coating film. The film thickness was about 0.1μ. As a result of measuring the transmittance of this glass plate at a wavelength of 550 nm, the untreated glass plate was 91.61, while the glass plate coated with the antireflection film was 93.9.
It was 2, and the antireflection effect was recognized.
【００３９】実施例４ 実施例１及び２で作成したフッ化マグネシウム水和物の
水性ゾル（Ｉ）（ＩＩ）及びイソプロピルアルコールゾ
ルをＭｇＦ2 濃度３％に希釈し、バーコーターにてガラ
ス板に塗布し、１１０℃で乾燥してフッ化マグネシウム
水和物の膜を形成させた。その膜厚は約０．１μであっ
た。このガラス板の５５０ｎｍ波長での透過率はそれぞ
れ９３．９８、９４．０５、９４．２８であり、透明
性、反射防止効果は良好であった。Example 4 The aqueous sol (I) (II) of magnesium fluoride hydrate and isopropyl alcohol sol prepared in Examples 1 and 2 were diluted to a MgF 2 concentration of 3%, and a glass plate was formed with a bar coater. It was applied and dried at 110 ° C. to form a film of magnesium fluoride hydrate. The film thickness was about 0.1 μ. The transmittance at 550 nm wavelength of this glass plate was 93.98, 94.05, and 94.28, respectively, and the transparency and antireflection effect were good.
【００４０】比較例１ 実施例１で調製したフッ化アンモニウム水溶液４１．４
ｋｇを２００リットルの容器に仕込み、ディスパーにて
強く撹拌しながら、室温で、実施例１で調製した塩化マ
グネシウム水溶液４２．４ｋｇを３０分間で添加した
後、更に１時間撹拌を続行し、フッ化マグネシウムのコ
ロイド粒子のスラリー８３．８ｋｇを得た。Comparative Example 1 Ammonium fluoride aqueous solution 41.4 prepared in Example 1
Into a 200 liter container, while stirring strongly with a disper, at room temperature, 42.4 kg of the magnesium chloride aqueous solution prepared in Example 1 was added over 30 minutes, and then the stirring was continued for another 1 hour, followed by fluorination. 83.8 kg of a slurry of magnesium colloidal particles was obtained.
【００４１】上記フッ化アンモニウムと塩化マグネシウ
ムのフッ素とマグネシウムの比は、Ｆ／Ｍｇモル比で
１．９８であった。得られたフッ化マグネシウムのコロ
イド粒子のスラリーは、白濁していて、フッ化マグネシ
ウムは大きな凝集体を形成した。このフッ化マグネシウ
ムのコロイド粒子のスラリー８３．８ｋｇは、チューブ
式限外ろ過装置を用いて、純水２７０ｋｇを限外ろ過速
度と同じ速度で添加しながら、ろ過洗浄を行った。Ｍｇ
Ｆ2としての濃度は５．０重量％で、電導度が３０５μ
ｓ／ｃｍになるまで充分に洗浄したが、大部分のフッ化
マグネシウムのコロイド粒子の凝集体はゾル化せず、ゾ
ル化率は１５％であった。ゾル化した部分はフッ化マグ
ネシウム水和物であった。The ratio of fluorine to magnesium in the above ammonium fluoride and magnesium chloride was 1.98 in terms of F / Mg molar ratio. The obtained slurry of magnesium fluoride colloidal particles was cloudy, and magnesium fluoride formed large aggregates. 83.8 kg of this magnesium fluoride colloidal particle slurry was filtered and washed using a tube type ultrafiltration device while adding 270 kg of pure water at the same rate as the ultrafiltration rate. Mg
The concentration as F 2 is 5.0% by weight and the electric conductivity is 305μ.
It was thoroughly washed to s / cm, but most aggregates of magnesium fluoride colloidal particles did not become a sol, and the solization rate was 15%. The solized portion was magnesium fluoride hydrate.
【００４２】[0042]
【発明の効果】本発明のフッ化マグネシウム水和物水性
ゾル及びフッ化マグネシウム水和物オルガノゾルは、電
子顕微鏡による観察で一次粒子径が１０〜１００ｎｍで
あり、良好な分散性を示す。このゾルの乾燥物は、Ｍｇ
Ｆ2 ・ｎＨ2 Ｏ( 但し、ｎは０．２５〜０．５）の組成
を示し、屈折率は１．３８５と低い。また、一次粒子径
が比較的大きいにもかかわらず、乾燥被膜は良好な光透
過性を示している。従って、このゾルを単独またはメチ
ルメタアクリルレートなどの有機樹脂の有機溶媒溶解
液、アクリル系やアクリルスチレン系などの有機樹脂エ
マルジョン、ポリビニルアルコールなどの水溶性高分子
水溶液、シランカップリング剤の部分加水分解液、エチ
ルシリケートの部分加水分解液、シリカゾルなどの他の
結合剤と混合使用することにより、ガラスレンズ、プラ
スチックレンズ、ガラス板、透明性プラスチック板、透
明プラスチックフィルム、陰極線管や液晶表示装置の画
像表示面、カラーフィルターなどに塗布することにより
良好な反射防止コート膜を形成することが出来る。INDUSTRIAL APPLICABILITY The magnesium fluoride hydrate aqueous sol and the magnesium fluoride hydrate organosol of the present invention have a primary particle diameter of 10 to 100 nm as observed by an electron microscope, and exhibit good dispersibility. The dried product of this sol is Mg
It has a composition of F 2 · nH 2 O (where n is 0.25 to 0.5) and has a low refractive index of 1.385. In addition, the dry coating film exhibits good light transmittance even though the primary particle diameter is relatively large. Therefore, this sol is used alone or in an organic solvent solution of an organic resin such as methylmethacrylate, an organic resin emulsion such as an acrylic or acrylic styrene type, a water-soluble polymer aqueous solution such as polyvinyl alcohol, or a partial hydrolysis of a silane coupling agent. Decomposition solution, partial hydrolysis solution of ethyl silicate, by mixing with other binders such as silica sol, glass lens, plastic lens, glass plate, transparent plastic plate, transparent plastic film, cathode ray tube and liquid crystal display device A good antireflection coating film can be formed by applying it to an image display surface, a color filter or the like.
【図１】実施例１で得られたフッ化マグネシウム水和物
水性ゾルを、１１０℃で乾燥した粉末のＸ線回折図。FIG. 1 is an X-ray diffraction diagram of a powder obtained by drying the magnesium fluoride hydrate aqueous sol obtained in Example 1 at 110 ° C.
【図２】実施例１で得られたフッ化マグネシウム水和物
水性ゾルを、５００℃で焼成した粉末のＸ線回折図。FIG. 2 is an X-ray diffraction pattern of a powder obtained by firing the magnesium fluoride hydrate aqueous sol obtained in Example 1 at 500 ° C.
【図３】実施例１で得られたフッ化マグネシウム水和物
水性ゾルを、１１０℃で乾燥した粉末の示差熱分析図。FIG. 3 is a differential thermal analysis diagram of a powder obtained by drying the magnesium hydrate hydrate aqueous sol obtained in Example 1 at 110 ° C.
１・・・示差熱分析（ＤＴＡ）の結果を示す曲線 ２・・・熱重量分析（ＴＧ）の結果を示す曲線 1 ... Curve showing the result of differential thermal analysis (DTA) 2 ... Curve showing the result of thermogravimetric analysis (TG)
Claims (3)
５〜０．５）の組成を有し、一次粒子径が１０〜１００
ｎｍであるフッ化マグネシウム水和物のコロイド粒子か
らなるゾル。1. MgF 2 .nH 2 O (where n is 0.2
5 to 0.5) and has a primary particle size of 10 to 100.
Sol consisting of colloidal particles of magnesium fluoride hydrate having a size of nm.
１．９〜２．０のＦ／Ｍｇモル比となる様に添加し、フ
ッ化マグネシウム水和物のコロイド粒子の凝集体スラリ
ーを生成させる工程、（ｂ） （ａ）工程により得られ
たフッ化マグネシウム水和物のコロイド粒子の凝集体ス
ラリー中の副生塩類を除去する工程、からなる請求項１
記載のフッ化マグネシウム水和物水性ゾルの製造法。2. The following steps (a) and (b): (a) An aqueous solution of magnesium salt and an aqueous solution of fluoride,
A step of adding an F / Mg molar ratio of 1.9 to 2.0 to form an aggregate slurry of colloidal particles of magnesium fluoride hydrate; 2. A step of removing by-product salts in a slurry of agglomerates of colloidal particles of magnesium iodide hydrate.
A method for producing an aqueous sol of magnesium fluoride hydrate described.
下記（ｃ）工程： （ｃ） （ｂ）工程により得られたフッ化マグネシウム
水和物水性ゾルの水を、溶媒置換法により有機溶媒に置
換する工程、からなる請求項１記載のフッ化マグネシウ
ム水和物オルガノゾルの製造法。3. The solvent replacement of the water of the magnesium fluoride hydrate aqueous sol obtained by the steps (a) and (b) and the following step (c) according to claim 2: (c) and (b) The method for producing a magnesium fluoride hydrate organosol according to claim 1, comprising the step of substituting an organic solvent by the method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21866693A JP3844787B2 (en) | 1993-09-02 | 1993-09-02 | Magnesium fluoride hydrate sol and its production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21866693A JP3844787B2 (en) | 1993-09-02 | 1993-09-02 | Magnesium fluoride hydrate sol and its production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0769621A true JPH0769621A (en) | 1995-03-14 |
| JP3844787B2 JP3844787B2 (en) | 2006-11-15 |
Family
ID=16723525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21866693A Expired - Fee Related JP3844787B2 (en) | 1993-09-02 | 1993-09-02 | Magnesium fluoride hydrate sol and its production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3844787B2 (en) |
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| JP2013245154A (en) * | 2012-05-29 | 2013-12-09 | Stella Chemifa Corp | Magnesium fluoride particle, method for producing magnesium fluoride particle, magnesium fluoride particle dispersion liquid, method for producing magnesium fluoride particle dispersion liquid, composition for forming low refractive index layer, method for producing composition for forming low refractive index layer, substrate with low refractive index layer, and method for producing substrate with low refractive index layer |
| WO2013180062A1 (en) * | 2012-05-29 | 2013-12-05 | ステラケミファ株式会社 | Magnesium fluoride particle, method for producing magnesium fluoride particle, magnesium fluoride particle dispersion, method for producing magnesium fluoride particle dispersion, composition for forming layer having low refractive index, method for producing composition for forming layer having low refractive index, substrate with layer having low refractive index, and method for producing substrate with layer having low refractive index |
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